Method of coloring hair with direct dye compounds

ABSTRACT

Described herein is a method of dyeing the hair. The method includes applying to the hair a hair color composition including one or more direct dye compounds and rinsing the hair with water. The one or more direct dye compounds each include a chromophore, one or two permanent cations, and one to four incipient cations. The one to four incipient cations are pendant to the core structure and are neutral. The one or more direct dye compounds enter the hair shaft after the hair color composition is applied to the hair. The hair color composition has a pH of from about 7 to about 11. The pH of the hair after rinsing is from about 3.5 to about 6. The rinsing of the hair causes one or more of the one to four incipient cations to change from neutral to positively charged inside of the hair shaft.

PRIORITY CLAIM

This application is a continuation of U.S. patent application Ser. No.15/072,496, filed on Mar. 17, 2016, which claims the benefit of priorityto U.S. Provisional Patent Application Ser. No. 62/135,513, filed onMar. 19, 2015, which applications are incorporated herein by referencein their entirety.

TECHNICAL FIELD OF THE INVENTION

Provided is a method of dyeing the hair with one or more washfast directdye compounds. The direct dye compounds each have one to four incipientcations. A decrease in pH when rinsing the hair causes one or more ofthe incipient cations to change from neutral to positively chargedinside of the hair shaft.

BACKGROUND OF THE INVENTION

In general, direct dye products last only 6-10 shampoos and are henceknown as semi-permanent. However, many consumers want more permanentresults, and therefore default to oxidative dye products that containhydrogen peroxide or other oxidants. The direct dye compounds and themethod described herein can be used in either direct dye or oxidationdye products.

The permanent alteration of the color of keratinous fibers, inparticular human hair, by the application of hair dyes is well known. Inorder to provide the consumer with the shade, longevity, and theintensity of color desired, an oxidative coloring process involvingcomplex chemical reactions is utilized. Permanent hair dyeingformulations typically comprise primary intermediates (also known asoxidative hair dye precursors or developers) and couplers (also known ascolor modifiers or secondary intermediates). These dye precursors aresufficiently small, polar and soluble to diffuse into the hair shaftwhere, once activated by an oxidizing agent under basic conditions, suchas hydrogen peroxide, the primary intermediates react with other dyeprecursors, e.g., couplers, to form larger colored chromophores in thehair shaft. The chromophores formed in the hair shaft do not readilydiffuse out of the hair during subsequent washing with water and/ordetergents because they are bigger, less polar and soluble than dyeprecursors that diffused in.

Hair colorant products are typically sold in the form of kits containinga dye component (e.g., a dye solution) and an oxidizing component (e.g.,a hydrogen peroxide solution). In use, the dye component is mixed withthe oxidizing component and the resultant mixture is applied to hair.When the two components are mixed, oxidizing agents present in theoxidizing component begins to oxidize primary inteunediates present inthe dye component and the oxidized primary intermediates begin to reactwith couplers to foiiii chromophores. Since coloring hair is one of thebeauty routines, it is highly desirable that the dyeing process,excluding bleaching, be rather a physical process, which would allow itto be aligned with many other beauty routines such as applying lip colorand facial touchups. The challenge is to still meet all of the otherrequirements of hair color (e,g., washfastness, little or no bleeding ofcolor from the hair when it is wet, evenness).

Many attempts have been made by the hair color industry to enhance thewashfastness of direct dyes by either foi ming a covalent bond betweenchromophore and proteins inside hair or increasing the number of bindingsites, typically cationic centers, on the chromophore. However, eachattempt has its drawbacks. The approach through covalent bonding doesnot differentiate proteins in hair from skin. The approach throughmultiple binding sites on the dyes (i,e multiple positive charges tointeract with negative sites on hair, either by bonding severalmonocationic dyes together or by installing multiple cationic centers ona single chromophore) runs into the obstacles of uneven color due touneven damage (negative charges) along the length of the hair fibers andreduced dye penetration into hair fibers because the dyes are typicallyat least twice as large as common oxidative dye precursors. An increasein the number of binding sites minimizes bleeding and color loss causedby rinsing by providing stronger hair-chromophore interactions. However,the same strong binding force to the cuticle also prevents thechromophores from penetrating deep into the cortex of hair, because itis difficult for dyes with multiple positive charges to diffuse throughnegatively charged networks of keratin proteins. Additionally, sincepolycationic dyes remain bound to the hair surface rather thanpenetrating into the fiber, it's difficult to produce dark shades due tolimited binding sites on the surface of hair.

Accordingly, there is a need for a direct dye compound with improved.washfa.stness without the drawbacks previously described.

SUMMARY OF THE INVENTION

Described herein is a method of dyeing the hair, the method comprising(a) applying to the hair a hair color composition comprising one or moredirect dye compounds, the one or more direct dye compounds eachcomprising (i) a chromophore; (ii) one or two permanent cations, whereinthe permanent cations are pendant to the chromophore or part of thechromophore, and wherein the chromophore and the permanent cations forma core structure; and (iii) one to four incipient cations, wherein theone to four incipient cations are pendant to the core structure, andwherein the incipient cations are neutral; wherein the one or moredirect dye compounds enter the hair shaft after the hair colorcomposition is applied to the hair; and wherein the hair colorcomposition has a pH of from about 7 to about 11; (b) rinsing the hairwith water; wherein the pH of the hair after rinsing is from about 3.5to about 6; and wherein the rinsing of the hair causes one or more ofthe one to four incipient cations to change from neutral to positivelycharged inside of the hair shaft.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified. When more than one composition is used during a treatment, asin mixing of the components of a typical oxidative dye product, thetotal weight to be considered is the total weight of all thecompositions applied on the hair simultaneously (i.e. the weight found“on head”) unless otherwise specified. The term “weight percent” may bedenoted as “wt. %” herein.

As used herein, the term “hair” to be treated may be “living” i.e. on aliving body or may be “non-living” i.e. in a wig, hairpiece or otheraggregation of non-living keratinous fibers. Mammalian, particularlyhuman, hair is preferred. However, wool, fur, and other keratincontaining fibers are suitable substrates for the compositions accordingto the present invention.

As used herein, the term “pendant group” means a group of atoms attachedto the core structure or chromophore. As described herein, the pendantgroup itself is not colored although it may influence the color of thechromophore. The pendant group may be further classified as an anchoringgroup or a hydrophobic group. A hydrophobic group is typically a carbonchain. An anchoring group is a group attached to either a permanentcation or incipient cation, occasionally it is attached to both apermanent cation and one or more incipient cations.

As used herein, the term “chromophore” means the part of the direct dyecompound responsible for its color.

As used herein, the term “direct dye compound” means a dye used in aprocess in which dye molecules are attracted by physical forces at themolecular level to a textile or substrate such as the hair. As opposedto oxidative dyes, there is no chemical reaction required to form thechromophore. Additionally, there is no covalent bond formation betweenthe direct dye and the substrate as opposed to reactive dyes. The directdye compound does not undergo a chemical transformation before and afterthe dyeing process.

As used herein, the term “core structure” means the chromophoreincluding one or two permanent cations that are pendant to thechromophore or part of the chromophore. In an embodiment, thechromophore is charged. In an embodiment, the chromophore is not chargedas the permanent cation is pendant to the chromophore.

As used herein, the term “pendant” means when a functional group islinked to a core structure via covalent bond.

As used herein, the teuii “incipient cation” means a functional groupthat goes from neutral to positively charged due to protonation causedby the decrease of pH.

As used herein, the term “non-anionic foaming agent” is a material thatfacilitates formation of foam. The term typically refers to a surfactantwhich, when present in small amounts, reduces the surface tension of aliquid or increases its colloidal stability by inhibiting coalescence ofbubbles.

The hair colorant compositions of the present invention comprise one ormore washfast direct dyes, optionally, oxidative dyes as well.

With regards to the direct dye compounds described herein, numeroustautomeric compounds may be involved. Thus, for example,2-mercaptopyridine (I) may exist under known conditions in thepyridine-2-thione tautomer form (II).

It is to be understood that when this development refers to a particularstructure, all of the reasonable additional tautomeric structures areincluded. In the art, tautomeric structures are frequently representedby one single structure and the method described herein follows thisgeneral practice.

It is also understood that within the scope of this invention, E, Zisomers may be involved. Thus, for example, (E)-diphenyldiazene (III)converts under known conditions to (Z)-diphenyldiazene (IV), which isalso reversible.

It is to be understood that when this development refers to a particularstructure, all of the reasonable additional E, Z isomers are included.

I. Washfast Direct Dyes

Described herein is a method of dyeing the hair, the method comprising(a) applying to the hair a hair color composition comprising one or moredirect dye compounds; the one or more direct dye compounds eachcomprising (i) a chromophore; (ii) one or two permanent cations, whereinthe permanent cations are pendant to the chromophore or part of thechromophore, and wherein the chromophore and the permanent cations forma core structure; and (iii) one to four incipient cations, wherein theone to four incipient cations are pendant to the core structure, andwherein the incipient cations are neutral; wherein the one or moredirect dye compounds enter the hair shaft after the hair colorcomposition is applied to the hair; and wherein the hair colorcomposition has a pH of from about 7 to about 11; (b) rinsing the hairwith water; wherein the pH of the hair after rinsing is from about 3.5to about 6; and wherein the rinsing of the hair causes one or more ofthe one to four incipient cations to change from neutral to positivelycharged inside of the hair shaft.

The one to four incipient cations, typically an amino group or groups,are attached to the chromophore in addition to the existing permanentcation(s) to overcome the problems encountered in previous attempts tomake cationic direct dyes more washfast. The chromophore would typicallycarry only one or two permanent positive charges such as quaternaryammonium salts, pyridinium, imidazolium, thiazolium, oxazolium,triazolium, pyrimidinium, triazinium, tetrazolium phenoxazinium,phenazinium or an analogous cation under basic conditions for typicalhair color applications. The amino group(s) would remain mostly neutralunder dyeing conditions (pH 10-11) because the typical pK_(a) ofaliphatic amines falls between 9-10.5. The dye would carry only one ortwo cationic charges under dyeing conditions, which provides the neededaffinity (Coulombic attraction) for optimized uptake without preventingpenetration due to relatively low charge density compared topolycationic dyes. However, once the coloring application is done andhair is rinsed, pH inside hair drops back to its natural pH, which isacidic, the amino group(s) attached to the chromophore would beprotonated to become an ammonium cation, which adds one or more bindingsites to the chromophore. The pH change functions as a convenient switchto turn on additional binding group(s) to make the chromophores morewashfast. Primary amines work the best when compared to secondary andtertiary amines for the following two reasons: 1. primary amines resistoxidation by hydrogen peroxide, while secondary and tertiary amines canbe oxidized and lose their anchoring capability when used together witha bleaching agent; 2. the protonated primary ammonium cation is thesmallest in size, which allows stronger interaction with anions on haircompared to secondary and tertiary amines with more steric hindrance.The following are examples of washfast dyes wherein one or moreincipient cations change from neutral to positively charged due to thedecrease of pH:

The linker groups, typically linear alkyl groups, would also function asmodulators for the overall hydrophobicity of the dye. One of the commondrawbacks of using exclusively cationic direct dyes for shading isoff-tone fading as different dyes would be washed off hair at differentrates, causing undesirable gradual color shift over time. Our technicalapproach minimizes off-tone fading by designing dyes of different colorswith identical charge patterns with similar overall hydrophobicity, atthe mean time, the fact that these inventive dyes are far more washfastthan typical cationic dyes also contributes to minimal color lost andon-tone fading.

The direct dye compounds may be substituted with one permanent cationiccharge, alternatively two permanent cationic charges. The direct dyecompounds may comprise and one to four termianl amino groups andderivatives thereof, alternatively two terminal amino groups andderivatives thereof, and alternatively one terminal amino group andderivatives thereof, according to the following formula:

The chemical formulas of the direct dye compounds can be represented inthe following ways, but not limited to what is shown below:

(L₂)_(y)-C*(-L₁-A)_(n) Z^(—)  (V)

(A₁-L_(i)-)_(n)C*(-L₂-A₂)_(m)(L₃)_(y)Z^(—)  (VI)

(Q*-L₃-)_(x)C(-L₁-A₁)_(m)(-L₂-A₂)_(n)(L₄)_(y)(Z^(—))_(x) or Z^(x)  (VII)

(L₃)_(y)-C(-L₁-Q*(-L₂-A)_(m))_(n)(Z^(—))_(n) or Z^(n—)  (VIII)

(L₂)_(y)-C*(-L₁-A₁-(L₃-A₂)_(m))_(n)Z^(—)  (IX)

wherein

C is a chromophore;

Q* is an organic cation;

* stands for a peimanent cationic charge, it can also be part of achromophore bearing a cationic charge;

L is a linker or hydrophobic chain and;

A is the anchoring group, the fastness enhancer. It is typically aprimary, secondary or tertiary amino group, preferably a primary amine.It is also a switch to allow the anchor to go between neutral andcharged states when the pH in the surrounding environment changes.

Z is a counter anion. It is typically a halide, sulfate, methylsulfate,hydrogen sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate,nitrate, perchlorate, tetrafluoroborate, hexafluorophosphate, triflate,acetate, formate or hydroxide.

n=1˜4; m=1˜4; n+m≤4; x=1˜2; y=0˜2

In some embodiments, C is of formula Xa

wherein

R_(1b), R_(1c), R_(1e), R_(1f), R_(1b) R_(1j) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(1h) and R_(1g) are each independently hydrogen, C₁-C₈ alkyl or linkergroup L with a primary, secondary or tertiary amino group attached; and

R_(1a) and R_(1d) are each independently C₁-C8 alkyl or linker group Lwith a primary, secondary or tertiary amino group attached;

The total number of amino groups attached to R_(1a), R_(1d), R_(1g) andR_(1h) is 1-4; the amino group can be primary, secondary or tertiary;and cosmetically acceptable salt thereof.

In some embodiments, L is of formula (XI)

wherein

L is covalently linked to the chromophore C of formula (Xa); L can belinked to C either by its left-hand or right-hand side.

a, c, e and g are each independently an integer from 0-3, provided thatthe sum of a, c, e and g is greater than or equal to 2; b, d and f areeach independently either 0 or 1; R₅₀, R₅₁, R₅₂, R₅₃, R₅₄, R₅₅, R₅₆ andR₅₇ are each independently hydrogen or C₁-C₂ alkyl group;

U is an aromatic ring, alkenyl or alkynyl moiety;

V is a hetero atom O, N or S;

W is a cyclic aliphatic ring.

In other embodiments, the chromophore C is of formula (Xb);

wherein

R_(2b), R_(2c), R_(2e), R_(2f), R_(2h), R_(2e) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(2g) is hydrogen, C₁-C₈ alkyl or linker group L with a primary,secondary or tertiary amino group attached; and

R_(2a) and R_(2d) are each independently C₁-C₈ alkyl or linker group Lwith a primary, secondary or tertiary amino group attached;

The total number of amino groups attached to R_(2a), R_(2d) and R_(2g)is 1-3; the amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xc);

wherein

R_(3b), R_(3c), R_(3d), R_(3e), R_(3h), R_(3i) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkenyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(3f) and R_(3g) are each independently hydrogen, C₁-C₈ alkyl or linkergroup L with a primary, secondary or tertiary amino group attached; and

R_(3a) is C₁-C₈ alkyl or linker group L with a primary, secondary ortertiary amino group attached;

The total number of amino groups attached to R_(3a), R_(3f) and R_(3g)is 1-3; the amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xd);

wherein

R_(4b), R_(4c), R_(4d), R_(4e), R_(4g), R_(4h) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a termianl amino group; and

R_(4f) is hydrogen, C₁-C₈ alkyl or linker group L with a primary,secondary or tertiary amino group attached; and

R_(4a) is C₁-C₈ alkyl or linker group L with a primary, secondary ortertiary amino group attached;

The total number of amino groups attached to R_(4a) and R_(4f) is 1 or2; the amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xe);

wherein

R_(5c), R_(5d), R_(5e), R_(5f), R_(5g), R_(5h) and R_(5i) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached tolinker L with or without a terminal amino group; and

R_(5a) is linker group L with a cationic moiety attached, the cationicgroup is quaternary ammonium, imidazolium, pyridinium, oxazolium orthiazolium; R_(5a) can also take on the following form asL₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different, Q* is thecationic moiety, A is an amino group and n is either 1 or 2; and

R_(5b) is a hydrogen, alkyl or linker group L with a primary, secondaryor tertiary amino group attached;

The total number of amino groups attached to R_(5a) and R_(5b) is 1, 2or 3; the amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xf);

wherein

R_(6c), R_(6d), R_(6e), R_(6g), R_(6h), R_(6i) and R_(6j) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached tolinker L with or without a terminal amino group; and

R_(6a) and R_(6e) are each independently linker group L with a cationicmoiety attached, the cationic group is quaternary ammonium, imidazolium,pyridinium, oxazolium or thiazolium; R_(6a) and R_(6e) can also eachindependently take on the following form as L₁-Q*(-L₂A)_(n), where L₁and L₂ can be the same or different, Q* is the cationic moiety, A is anamino group and n is either 1 or 2; and

R_(6b) and R_(6f) are each independently a hydrogen, alkyl or linkergroup L with a primary, secondary or tertiary amino group attached;

The total number of amino groups attached to R_(6a), R_(6b), R_(6e) andR_(6f) is 1, 2, 3 or 4; amino group can be primary, secondary ortertiary; the total number of cationic moiety attached to R_(6a) andR_(6e) is 1 or 2; and cosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xg);

wherein

R_(7b), R_(7c), R_(7d), R_(7f), R_(7g), R_(7h), R_(7i), R_(7j), R_(7k)and R_(7m) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L with or without a terminal amino group; and

R_(7a) and R_(7e) are each independently C₁-C₈ alkyl or a linker group Lwith a primary, secondary or tertiary amino group attached; and

The total number of amino groups attached to R_(7a) and R_(7e) is 1 or2; amino group can be primary, secondary or tertiary; and cosmeticallyacceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xh);

wherein

R_(8b), R_(8c), R_(8d), R_(8h) and R_(8i) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(8a) and R_(8g) are each independently C₁-C₈ alkyl or linker group Lwith a primary, secondary or tertiary amino group attached; and

R_(8e) and R_(8f) are each independently hydrogen, C₁-C₈ alkyl, hydroxylalkyl or linker group L with a primary, secondary or tertiary aminogroup attached; and

The total number of amino groups attached to R_(8a), R_(8g), R_(8e) andR_(8f) is 1-4; amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xi);

wherein

R_(9b), R_(9c), R_(9g), R_(9h) and R_(9i) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(9a) and R_(9f) are each independently C₁-C₈ alkyl or linker group Lwith a primary, secondary or tertiary amino group attached; and

R_(9d) and R_(9e) are each independently hydrogen, C₁-C₈ alkyl, hydroxylalkyl or linker group L with a primary, secondary or tertiary aminogroup attached; and

The total number of amino groups attached to R_(9a), R_(9d), R_(9e) andR_(9f) is 1-4; amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xj);

wherein

R_(10b), R_(10c), R_(10d), R_(10e) and R_(10i) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(10a) and R_(10h) are each independently C₁-C₈ alkyl or linker group Lwith a primary, secondary or tertiary amino group attached; and

R_(10f) and R_(10g) are each independently hydrogen, C₁-C₈ alkyl,hydroxyl alkyl or linker group L with a primary, secondary or tertiaryamino group attached; and

The total number of amino groups attached to R_(10a), R_(10f), R_(10g)and R_(10h) is 1-4; amino group can be primary, secondary or tertiary;and cosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xk);

wherein

R_(11b), R_(11c), R_(11d), R_(11e), R_(11f), R_(11i), R_(11j) andR_(11k) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L with or without a terminal amino group; and

R_(11a) is C₁-C₃ alkyl or linker group L with a primary, secondary ortertiary amino group attached; and

R_(11g) and R_(11h) are each independently hydrogen, C₁-C₃ alkyl,hydroxyl alkyl or linker group L with a primary, secondary or tertiaryamino group attached; and

The total number of amino groups attached to R_(11a), R_(11g) andR_(11h) is is 1-3; amino group can be primary, secondary or tertiary;and cosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (XI);

wherein

R_(12b), R_(12c), R_(12d), R_(12e), R_(12h), R_(12i), R_(12j) andR_(12k) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L with or without a terminal amino group; and

R_(12a) is C₁-C₈ alkyl or linker group L with a primary, secondary ortertiary amino group attached; and

R_(12f) and R_(12g) are each independently hydrogen, C₁-C₈ alkyl,hydroxyl alkyl or linker group L with a primary, secondary or tertiaryamino group attached; and

The total number of amino groups attached to R_(12a), R_(12f) andR_(12g) is 1-3; amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xm);

wherein

R_(13b), R_(13c), R_(13d), R_(13e), R_(13f), R_(13g), R_(13j) andR_(13k) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L with or without a terminal amino group; and

R_(13a) is C₁-C₈ alkyl or linker group L with a primary, secondary ortertiary amino group attached; and

R_(13h) and R_(13i) are each independently hydrogen, C₁-C₈ alkyl,hydroxyl alkyl or linker group L with a primary, secondary or tertiaryamino group attached; and

The total number of amino groups attached to R_(13a), R_(13f) andR_(13g) is 1-3; amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xn);

wherein

R_(14b), R_(14c), R_(14d), R_(14e), R_(14h), R_(14i), R_(14j), R_(14k),R_(14l) and R_(14m) are each independently hydrogen, alkyl, halogensubstituted alkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy,aryloxy, acyl, halogen, nitro, nitroso, cyano, a heterocyclic moiety,thioether or are attached to linker L with or without a terminal aminogroup; and

R_(14a) is C₁-C₈ alkyl or linker group L with a primary, secondary ortertiary amino group attached; and

R_(14g) and R_(14f) are each independently hydrogen, C₁-C₈ alkyl,hydroxyl alkyl or linker group L with a primary, secondary or tertiaryamino group attached; and

The total number of amino groups attached to R_(14a), R_(14f) andR_(14g) is 1-3; amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xo);

wherein

R_(15b), R_(15c), R_(15d), R_(15e), R_(15g), R_(15h), R_(15k) andR_(15l) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L with or without a terminal amino group; and

R_(15a) and R_(15f) are each independently C₁-C₈ alkyl or linker group Lwith a primary, secondary or tertiary amino group attached; and

R_(15i) and R_(15j) are each independently hydrogen, C₁-C₈ alkyl,hydroxyl alkyl or linker group L with a primary, secondary or tertiaryamino group attached; and

The total number of amino groups attached to R_(15a), R_(15f), R_(15i)and R_(15j) is 1-4; amino group can be primary, secondary or tertiary;and cosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xp);

wherein

R_(16c), R_(16d), R_(16e) and R_(16f) are each independently hydrogen,alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl, hydroxylalkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(16a) is linker group L with a cationic moiety attached, the cationicgroup is quaternary ammonium, imidazolium, pyridinium, oxazolium orthiazolium; R_(16a) can also take on the following form asL₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different, Q* is thecationic moiety, A is an amino group; and n is either 1 or 2; and

R_(16b) is a hydrogen, alkyl or linker group L with a primary, secondaryor tertiary amino group attached;

The total number of amino groups attached to R_(16a) and R_(16b) is 1, 2or 3; the amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xq);

wherein

R_(17c), R_(17d), R_(17e) and R_(17f) are each independently hydrogen,alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl, hydroxylalkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L with orwithout a terminal amino group; and

R_(17a) is linker group L with a cationic moiety attached, the cationicgroup is quaternary ammonium, imidazolium, pyridinium, oxazolium orthiazolium; R_(17a) can also take on the following form asL₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different, Q* is thecationic moiety, A is an amino group; and n is either 1 or 2; and

R_(17b) is a hydrogen, alkyl or linker group L with a primary, secondaryor tertiary amino group attached;

The total number of amino groups attached to R_(17a) and R_(17b) is 1, 2or 3; the amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xr);

wherein

R_(18c), R_(18d) and R_(18f) are each independently hydrogen, alkyl,halogen substituted alkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl,alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, a heterocyclicmoiety, thioether or are attached to linker L with or without a terminalamino group; and

R_(18a) is linker group L with a cationic moiety attached, the cationicgroup is quaternary ammonium, imidazolium, pyridinium, oxazolium orthiazolium; R_(18a) can also take on the following form asL₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different, Q* is thecationic moiety, A is an amino group; and n is either 1 or 2; and

R_(18b) and R_(18e) are each independently a hydrogen, alkyl or linkergroup L with a primary, secondary or tertiary amino group attached;

The total number of amino groups attached to R_(18a), R_(18b) andR_(18c) is 1, 2 or 3; the amino group can be primary, secondary ortertiary; and cosmetically acceptable salt thereof.

In other embodiments, the chromophore C is of formula (Xs);

wherein

R_(19c), R_(19d) and R_(19g) are each independently hydrogen, alkyl,halogen substituted alkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl,alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, a heterocyclicmoiety, thioether or are attached to linker L with or without a terminalamino group; and

One of R_(19a) and R_(19e) is linker group L with a cationic moietyattached, the cationic group is quaternary ammonium, imidazolium,pyridinium, oxazolium or thiazolium; it can also take on the followingform as L₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different,Q* is the cationic moiety, A is an amino group; and n is either 1 or 2;and the other one is a hydrogen, alkyl, hydroxyl alkyl or attached to anamino group through linker L; and

R_(19b) and R_(19e) are each independently a hydrogen, alkyl, hydroxylalkyl or linker group L with a primary, secondary or tertiary aminogroup attached;

The total number of amino groups attached to R_(19a), R_(19b), R_(19e)and R_(19f) is 1-4; the amino group can be primary, secondary ortertiary; and cosmetically acceptable salt thereof.

The following are examples of the synthesis of various washfast directdye compounds as described herein:

EXAMPLE 1

In example 1, the pei manent cation is part of the chromophore andresides on the imidazolium moiety. The incipient cations are linked tothe chromophore via ethylene groups.

Method 2-((4-methoxyphenyl)diazenyl)-1,3-dimethyl-1H-imidazol-3-iumiodide (500 mg) was suspended in isopropanol (20 mL), then addeddropwise to 10 eq. of tris(2-aminoethyl)amine in refluxing isopropanol(100 mL) to produce the red dye2-((4-((2-(bis(2-aminoethyl)amino)ethyl)amino)phenyl)diazenyl)-1,3-dimethyl-1H-imidazol-3-iumiodide in near quantitative yield. The desired red dye was purified onpreparative HPLC with C18 reverse phase column and water/acetonitrile(with 0.1% TFA) as mobile phase. The final product (XII) was collectedas a trifluoroacetate salt.

-   ¹ H NMR: (600.1 MHz, D₂O) δ=2.84 (2 H, t, J=6.4 Hz), 2.86 (4 t,    J=6.4 Hz), 3.05 (4 H, t, J=6.4 Hz), 3.41 (2 H, t, J=6.4 Hz), 3.88 (6    H, s), 6.74 (2 H, d, J=9.1 Hz), 7.28 (2 H, s), 7.85 (2 H, d, J=8.9    Hz).-   ¹³C NMR: (150.9 MHz, D₂O) δ=35.82, 36.79, 39.58, 50.30, 51.00,    112.83, 116.37 (q, J_(C-F)=292.7 Hz), 122.30, 144.69, 145.21,    155.73, 162.93 (q, J_(C-F)=35.2 Hz).

EXAMPLE 2

In example 2, the permanent cation is not part of the chromophore. It islinked to the chromophore via an ethylene group. Incipient cations areconnected to the chromophore via the permanent cation.

Method

1,4-Difluoroanthraquinone (240 mg) was mixed withN,N-tris(2-aminoethyl)-N-methylammonium chloride (1.1 eq.) in DMSO (20mL). The mixture was heated at 85° C. for 12 hours until all thedifluoroanthraquinone had been consumed. The resulting red dye2-amino-N-(2-aminoethyl)-N-(2-((4-fluoro-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino)ethyl)-N-methylethan-1-aminiumsalt was purified on C18 reverse phase column with water/acetonitrile(with 0.1% TFA) as mobile phase. The final product (XIII) was collectedas its corresponding trifluoroacetate salt.

-   ¹H NMR: (600.1 MHz, D₂O) δ=3.38 (3 H, s), 3.59 (4 H, t, J=8.2 Hz),    3.77 (4 H, dd, J₁=9.4 Hz, J₂=4.6 Hz), 3.85-3.93 (4 H, m), 6.85 (1 H,    dd, J₁=9.5 Hz, J₂=3.8 Hz), (1 H, dd, J₁=11.3 Hz, J₂=9.8 Hz),    7.50˜7.56 (3 H, m), 7.65˜7.66 (I H, m).-   ¹³C NMR: (150.9 MHz, D₂O) δ=32.42, 35.97, 49.51, 58.24, 61.86,    111.34, 116.31 (q, J_(C-F)=291.6 Hz) 118.65, 121.05 (d, J_(C-F)=8.81    Hz), 126.20 (d, J_(C-F)=17.6 Hz), 126.79 (d, J_(C-F)=26.4 Hz),    131.93, 132.64, 134.07, 134.83, 147.18, 152.85, 154.57, 162.79 (q,    J_(C-F)=35.6 Hz), 182.69, 184.30 (d, J_(C-F)=4.41 Hz).

EXAMPLE 3

The dye in example 3 is constructed in a similar fashion as in example2, but with twice the anchoring power. The color is blue instead of red.

Method

1,4-Difluoroanthraquinone was treated with 4 eq. oftris(2-aminoethyl)amine in DMSO, the mixture was heated until allanthraquinone starting material was consumed. The resulting blue dye,1,4-bis((2-(bis(2-aminoethyl)amino)ethyl)amino)anthraquinone, wastreated with (Boc)₂O to yield tetra Boc protected intermediate, whichwas then quaternized with Mel in acetonitrile. The Boc group was removedby HCl to yield the final product,2,2′-((anthraquinone4,4-diyl)bis(azanediyl))bis(N,N-bis(2-aminoethyl)-N-methylethan-1-ammonium)chloride.

-   ¹H NMR: (600.1 MHz, D₂O) δ=3.39 (6 H, s), 3.57 (8 H, t, 8.3 Hz),    3.86-3.93 (12 H, m), 3.96 (4 H, t, J=6.2 Hz), 7.01 (2 H, s), 7.64 (2    H, dd, J₁=5.9 Hz, J₂=3.3 Hz), 7.81 (2 H, dd, J₁=5.8 Hz, J₂=3.4 Hz).-   ¹³C NMR: (150.9 MHz, D₂O) δ=32.62, 36.08, 49.77, 58.19, 62.42,    110.42, 124.23, 125.82, 133.15, 133.34, 144.97, 182.93.

Exemplary Formulations

% by weight Composition A Washfast Direct Dye¹ 0.50 Ammonium Hydroxide(aq. 28% active) 4.50 Water 95.00 Composition B Washfast Direct Dye¹0.50 Ammonium carbonate 10.00 Water 89.50 Composition C Washfast DirectDye¹ 0.50 FlexiThix ™ ³ 5.00 Phenoxyethanol 0.30 Sodium Benzoate 0.30Disodium EDTA 0.10 Ammonium Hydroxide (aq. 28% active) 4.00 Water 89.80Composition D Washfast Direct Dye¹ 0.50 Aculyn ™ 46⁴ 15.80Phenoxyethanol 0.30 Sodium Benzoate 0.30 Disodium EDTA 0.10 AmmoniumHydroxide (aq. 28% active) 4.00 Water 79.00 Composition E WashfastDirect Dye¹ 0.50 Plantaren ® 2000 N UP² 20.00 Phenoxyethanol 0.30 SodiumBenzoate 0.30 Disodium EDTA 0.10 Ammonium Hydroxide (aq. 28% active)4.00 Water 74.80 Composition F Washfast Direct Dye¹ 0.50 Non-anionicfoaming agent 5.00 Phenoxyethanol 0.30 Sodium Benzoate 0.30 DisodiumEDTA 0.10 Ammonium Hydroxide (aq. 28% active) 4.00 Water 89.80 ¹Thewashfast direct dye may be any washfast direct dye described herein²(chemical makeup supplied by BASF) ³ PVP polymer supplied by Ashland⁴PEG-150/Stearyl/SMDI copolymer supplied by Rhom and Haas

The hair color compositions described herein may be formed as thickliquid, cream, gel, emulsion, foam, aerosol mousse or as a solid form towhich water is added to generate the oxidant and form a thickenedvehicle suitable for hair coloring. They may comprise in addition to theingredients indicated above further ingredients in order to furtherenhance the properties of the composition, including but not limited to:solvents; oxidative dyes, direct dyes; oxidizing agents; radicalscavengers; thickeners and or rheology modifiers; chelants; pH modifiersand buffering agents; carbonate ion sources; peroxymonocarbonate ionsources; anionic, cationic, nonionic, amphoteric or zwitterionicsurfactants, or mixtures thereof, anionic, cationic, nonionic,amphoteric or zwitterionic polymers, or mixtures thereof; fragrances;enzymes; dispersing agents; peroxide stabilizing agents; antioxidants;natural ingredients, e.g. proteins and protein compounds, and plantextracts; conditioning agents including silicones and cationic polymers,ceramides, preserving agents; and opacifiers and pearling agents (suchas titanium dioxide and mica). Some adjuvants referred to above, but notspecifically described below, which are suitable are listed in theInternational Cosmetics Ingredient Dictionary and Handbook, (8th ed.;The Cosmetics, Toiletry, and Fragrance Association). Particularly, vol.2, sections 3 (Chemical Classes) and 4 (Functions) are useful inidentifying specific adjuvants to achieve a particular purpose ormultipurpose. A few of these ingredients are discussed hereinbelow,whose disclosure is of course non-exhaustive.

Optional Ingredients

The hair color compositions described herein may comprise, in additionto the ingredients indicated above, optional ingredients in order tofurther enhance the properties of the composition.

Suitable optional ingredients include, but are not limited to: solvents;oxidizing agents; alkalizing agents; oxidative dye precursors, directdyes; chelants; radical scavengers; pH modifiers and buffering agents;thickeners and/or rheology modifiers; carbonate ion sources;peroxymonocarbonate ion sources; anionic, cationic, nonionic, amphotericor zwitterionic surfactants, and mixtures thereof; anionic, cationic,nonionic, amphoteric or zwitterionic polymers, and mixtures thereof;fragrances; enzymes; dispersing agents; peroxide stabilizing agents;antioxidants; natural ingredients (such as proteins, protein compounds,and plant extracts); conditioning agents (such as silicones and cationicpolymers); ceramides; preserving agents; opacifiers and pearling agents(such as titanium dioxide and mica); and mixtures thereof. Suitablefurther ingredients referred to above, but not specifically describedbelow, are listed in the International Cosmetics Ingredient Dictionaryand. Handbook, (8th ed.; The Cosmetics, Toiletry, and FragranceAssociation). Particularly, vol. 2, sections 3 (Chemical Classes) and 4(Functions), which are useful in identifying specific adjuvants toachieve a particular purpose or multipurpose. A few of these ingredientsare discussed hereinbelow, whose disclosure is of course non-exhaustive.

Solvents

The hair color compositions described herein may further comprise asolvent. The solvent may be selected from water, or a mixture of waterand at least one organic solvent to dissolve the compounds that wouldnot typically be sufficiently soluble in water.

Suitable organic solvents include, but are not limited to: C1 to C4lower alkanols (such as ethanol, propanol, isopropanol); aromaticalcohols (such as benzyl alcohol and phenoxyethanol); polyols and polyolethers (such as carbitols, 2-butoxyethanol, propylene glycol, propyleneglycol monomethyl ether, diethylene glycol monoethyl ether, monomethylether, hexylene glycol, glycerol, ethoxy glycol, butoxydiglycol,ethoxydiglycerol, dipropyleneglocol, polygylcerol); propylene carbonate;and mixtures thereof.

In an embodiment, the solvent may be selected from the group consistingof water, ethanol, propanol, isopropanol, glycerol, 1,2-propyleneglycol, hexylene glycol, ethoxy diglycol, and mixtures thereof.

The composition may comprise water as a main ingredient, particularly ina. total amount ranging from at least about 50%, alternatively from atleast about 60%, alternatively from at least about 70%, by weight of thetotal composition. In an embodiment, the composition may comprise atotal amount of organic solvents ranging from about 1% to about 30%, byweight of the total hair color composition.

Oxidizing Agent

The hair color composition described herein may comprise at least onesource of an oxidizing agent. Preferred oxidizing agents for use hereinare water soluble peroxygen oxidizing agents. Water-soluble peroxygenoxidizing agents are well known in the art and include, but are notlimited to, hydrogen peroxide, inorganic alkali metal peroxides such assodium periodate and sodium peroxide and organic peroxides such as ureaperoxide, melamine peroxide, and inorganic perhydrate salt bleachingcompounds, such as the alkali metal salts of perborates, percarbonates,perphosphates, persilicates, persulfates and the like. These inorganicperhydrate salts may be incorporated as monohydrates, tetrahydrates etc.Alkyl and aryl peroxides, and or peroxidases, oxidases, and uricases andtheir substrates may also be used. Mixtures of two or more suchoxidizing agents can also be used if desired. The oxidizing agents maybe provided in aqueous solution or as a powder which is dissolved priorto use. In an embodiment, the oxidizing agents may be selected from thegroup consisting of hydrogen peroxide, percarbonate, persulfates andcombinations thereof.

In an embodiment, the hair color composition may comprise from 0.1% to20% by weight, or from 1% to 15% by weight, or from 2% to 10% by weightof the oxidizing agent.

A potential oxidizing agent for use herein is a source ofperoxymonocarbonate ions formed in situ from a source of hydrogenperoxide and a hydrogen carbonate ion source. Moreover, this system isalso particularly effective in combination with a source of ammonia orammonium ions. Accordingly, any source of these peroxymonocarbonate ionsmay be used. Suitable sources for use herein include sodium, potassium,guanidine, arginine, lithium, calcium, magnesium, barium, ammonium saltsof carbonate, carbamate and hydrocarbonate ions and mixtures thereofsuch as sodium carbonate, sodium hydrogen carbonate, potassiumcarbonate, potassium hydrogen carbonate, guanidine carbonate, guanidinehydrogen carbonate, lithium carbonate, calcium carbonate, magnesiumcarbonate, barium carbonate, ammonium carbonate, ammonium hydrogencarbonate and mixtures thereof. Percarbonate salts may be used both asan oxidizing agent and as a source of carbonate ions. Preferred sourcesof carbonate ions, carbamate and hydrocarbonate ions are sodium hydrogencarbonate, potassium hydrogen carbonate, ammonium carbamate, andmixtures thereof.

The oxidizing agent may comprise from 0.1% to 15% by weight, or from 1%to 10% by weight, or from 1% to 8% by weight of a hydrogen carbonateion; and from 0.1% to 10% by weight, or from 1% to 7% by weight, or from2% to 5% by weight of the oxidizing agent of a source of hydrogenperoxide.

Alkalizing Agent

The hair color composition described herein may further comprise analkalizing agent as known in the art. Any alkalizing agent known in theart may be used such as ammonia, alkanolamines for examplemonoethanolamine, diethanolamine, triethanolamine, monopropanolamine,dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol,2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3-propanediol, guanidium salts, alkali metaland ammonium hydroxides such as sodium hydroxide, alkali metal andammonium carbonates, and mixtures thereof In an embodiment, thealkalizing agent may be ammonia and/or monoethanolamine.

The hair color compositions described herein may comprise from about0.1% to about 10%, preferably from about 0.5% to about 6%, morepreferably from about 1% to about 4% by weight of the alkalizing agentrelative to the total weight of the composition.

The hair colorant compositions described above may have a pH of from 7to 12, alternatively from 8 to 11. For embodiments comprising aperoxymonocarbonate ion, the pH may be up to and including pH 9.5,alternatively from 7.5 to 9.5, alternatively from 8.4 to 9.5,alternatively from 8.5 to 9.4, alternatively 9.0, and alternatively 9.3.

Any sub-components of the hair color compositions, such as a tintcomposition or an oxidizing composition, may have a different pH fromthe hair colorant composition. For example, if the tint compositioncomprises an alkalizing agent, the tint composition will have analkaline pH, such as higher than 7. In an embodiment, the oxidizingcomposition may comprise an acidic pH of less than 7.

When the hair color composition described herein is obtained by mixing adeveloper and a tint composition prior to use, the alkalizing agent isgenerally present in the tint composition.

Oxidative Dye Precursors

In addition to the direct dye compounds described herein, the hair colorcomposition may further comprise one or more oxidative dye precursors,which are usually classified either as primary intermediates (also knownas developers) or couplers (also known as secondary intennediates).Various couplers may be used with primary intermediates in order toobtain different shades. Oxidative dye precursors may be free bases orthe cosmetically acceptable salts thereof

In an embodiment, the hair color composition may comprise a total amountof oxidative dye precursors ranging up to about 12%, alternatively fromabout 0.1% to about 10%, alternatively from about 0.3% to about 8%,alternatively from about 0.5% to about 6%, by weight of the totalcomposition.

Suitable primary intermediates include, but are not limited to:toluene-2,5-diamine, p-phenylenediamine, N-phenyl-p-phenylenediamine,N,N-bis(2-hydroxyethyl-p-phenylenediamine,2-hydroxyethyl-p-phenylenediamine), 2-methoxymethyl-p-phenylenediamine,2-(1,2-dihydroxyethyl)-p-phenylenediamine,2,2′-(2-(4-aminophenylamino)ethylazanediyl)diethanol,2-(2,5-diamino-4-methoxyphenyl)propane-1,3-diol,2-(7-amino-2H-benzo[b][1,4]oxazin-4(3H)-yl)ethanol,2-chloro-p-phenylenediamine, p-aminophenol, p-(methylamino)phenol,4-amino-m-cresol, 6-amino-m-cresol, 5-ethyl-o-aminophenol,2-methoxy-p-phenylenediamine, 2,2′-methylenebis-4-aminophenol,2,4,5,6-tetraminopyrimidine, 2,5,6-triamino-4-pyrimidinol,1-hydroxyethyl-4,5-diaminopyrazole sulfate,4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole,4,5-diatnino-1-isopropylpyrazole, 4,5-diamino-1-butylpyrazole,4,5-diamino-1-pentylpyrazole, 4,5-diamino-1-benzylpyrazole,(2,3-diarnino-6,7-dihydro-1H, 5H-pyrazolo[1,2-a]pyrazol-1-onedimethanesulfonate), 4,5-diamino-1-hexylpyrazole,4,5-diamino-1-heptylpyrazole, methoxymethyl-1,4-diaminobenzene,N,N-bis(2-hydroxyethyl)-N-(4-aminophenyl)-1,2-diaminothane,2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride, saltsthereof and mixtures thereof.

Suitable couplers include, but are not limited to: resorcinol,4-chlororesorcinol, 2-chlororesorcinol, 2-methylresorcinol,4,6-dichlorobenzene-1,3-diol, 2,4-dimethylbenzene-1,3-diol,m-aminophenol, 4-amino-2-hydroxytoluene,2-methyl-5-hydroxyethylaminophenol, 3-amino-2,6-dimethylphenol,3-amino-2,4-dichlorophenol, 5-amino-6-chloro-o-cresol,5-amino-4-chloro-o-cresol, 6-hydroxybenzomorpholine,2-amino-5-ethylphenol, 2-amino-5-phenylphenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 2-amino-5-ethoxyphenol,5-methyl-2-(methylamino)phenol, 2,4-diaminophenoxyethanol,2-amino-4-hydroxyethylaminoanisole,1,3-bis-(2,4-diaminophenoxy)-propane,2,2′-(2-methyl-1.3-phenylene)bis(azanediyl)diethanol,benzene-1,3-diamine, 2,2′-(4,6-diamino-1,3-phenylene)bis(oxy)diethanol,3-(pyrrolidin-1-yl)aniline, 1-(3-(dimethylamino)phenyl)urea,1-(3-aminophenyl)urea, 1-naphthol, 2-methyl-1-naphthol, 1,5-naphthalenediol, 2,7-naphthalenediol orl-acetoxy-2-methylnaphthalene,4-chloro-2-methylnaphthalen-1-ol, 4-methoxy-2-methylnaphthalen-1-ol,2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine,3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine,2,6-diaminopyridine, pyridine-2,6-diol, 5,6-dihydroxyindole,6-hydroxyindole, 5,6-dihydroxyindoline,3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, 1,2,4-trihydroxybenzene,2-(benzo[d][1,3]dioxo1-5-ylamino)ethanol (also known ashydroxyethyl-3,4-methylenedioxyaniline), and mixtures thereof.

When the hair color composition described herein is obtained by mixing atint composition and a developer composition, the primary intermediatesand couplers may be incorporated into the tint composition.

Additional Direct Dyes

The hair color composition may further comprise additional compatibledirect dyes, in an amount sufficient to provide additional coloring,particularly with regard to intensity. In an embodiment, the compositionmay comprise a total amount of direct dyes ranging from about 0.05% toabout 4%, by weight of the total composition.

Suitable direct dyes include but are not limited to: Acid dyes such asAcid Yellow 1, Acid Orange 3, Acid Black 1, Acid Black 52, Acid Orange7, Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Violet 43, HC Blue 16,Acid Blue 62, Acid Blue 25, Acid Red 4; Basic Dyes such as Basic Brown17, Basic Red 118, Basic Orange 69, Basic Red 76, Basic Brown 16, BasicYellow 57, Basic Violet 14, Basic Blue 7, Basic Blue 26, Basic Red 2,Basic Blue 99, Basic Yellow 29, Basic Red 51, Basic Orange 31, BasicYellow 87, Basic Blue 124,4-(3-(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl)-4-methylmorpholin-4-ium-methylsulfate,(E)-1-(2-(4-(4,5-dimethylthiazol-2-yl)diazenyl)phenyl)(ethyl)amino)ethyl)-3-methyl-1H-imidazol-3-iumchloride,(E)-4-(2-(4-(dimethylamino)phenyl)diazenyl)-1-methyl-1H-imidazol-3-ium-3-yl)butane-1-sulfonate,(E)-4-(4-(2-methyl-2-phenylhydrazono)methyl)pyridinium-1-yl)butane-1-sulfonate,N,N-dimethyl-3-(4-(methylamino)-9,10-dioxo-4a,9,9a,10-tetrahydroanthracen-1-ylamino)-N-propylpropan-1-aminiumbromide; Disperse Dyes such as Disperse Red 17, Disperse Violet 1,Disperse Red 15, Disperse Black 9, Disperse Blue 3, Disperse Blue 23,Disperse Blue 377; Nitro Dyes such asl-(2-(4-nitrophenylamino)ethyl)urea,2-(4-methyl-2-nitrophenylamino)ethanol, 4-nitrobenzene-1,2-diamine,2-nitrobenzene-1,4-diamine, Picramic acid, HC Red No. 13,2,2′-(2-nitro-1,4-phenylene)bis(azanediyl)diethanol, HC Yellow No. 5, HCRed No. 7, HC Blue No.2, HC Yellow No. 4, HC Yellow No. 2, HC Orange No.1, HC Red No. 1, 2-(4-amino-2-chloro-5-nitrophenylamino)ethanol, HC RedNo. 3, 4-amino-3-nitrophenol, 4-(2-hydroxyethylamino)-3-nitrophenol,2-amino-3-nitrophenol, 2-(3-(methylamino)-4-nitrophenoxy)ethanol,3-(3-amino-4-nitrophenyl)propane-1,2-diol, HC Yellow No. 11, HC VioletNo. 1, HC Orange No. 2, HC Orange No. 3, HC Yellow No. 9, HC Red No. 10,HC Red No. 11, 2-(2-hydroxyethylamino)-4,6-dinitrophenol, HC Blue No.12, IIC Yellow No. 6, FTC Yellow No. 12, HC Blue No. 10, HC Yellow No.7, HC Yellow No. 10, HC Blue No. 9,2-chloro-6-(ethylamino)-4-nitrophenol, 6-nitropyridine-2,5-diamine, FTCViolet No. 2, 2-amino-6-chloro-4-nitrophenol,4-(3-hydroxypropylamino)-3-nitrophenol, BC Yellow No. 13,6-nitro-1,2,3,4-tetrahydroquinoxaline, HC Red No. 14, HC Yellow No. 15,HC Yellow No. 14, N2-methyl-6-nitropyridine-2,5-diamine,N1-allyl-2-nitrobenzene-1,4-diamine, HC Red. No. 8, HC Green No.1, HCBlue No. 14; Natural dyes such as Annato, Anthocyanin, Beetroot,Carotene, Capsanthin, Lycopene, Chlorophyll, Henna, Indigo, Cochineal;and mixtures thereof.

When the hair color composition is obtained by mixing a tint compositionand a developer composition, the additional direct dyes may beincorporated into the tint composition.

Chelants

The hair color composition described herein may further comprisechelants (also known as “chelating agent”, “sequestering agent”, or“sequestrant”) in an amount sufficient to reduce the amount of metalsavailable to interact with formulation components, particularlyoxidizing agents, more particularly peroxides. Chelants are well knownin the art and a non-exhaustive list thereof can be found in A E Martell& R M Smith, Critical Stability Constants, Vol. 1, Plenum Press, NewYork & London (1974) and A E Martell & R D Hancock, Metal Complexes inAqueous Solution, Plenum Press, New York & London (1996), bothincorporated herein by reference.

In an embodiment, the hair color composition may comprise a total amountof chelants ranging from at least about 0.01%, alternatively from about0.01% to about 5%, alternatively from about 0.25% to about 3%,alternatively from about 0.5% to about 1%, by weight of the totalcomposition.

Suitable chelants include, but are not limited to: carboxylic acids(such as aminocarboxylic acids), phosphonic acids (such asaminophosphonic acids), polyphosphoric acids (such as linearpolyphosphoric acids), their salts thereof, and mixtures thereof. By“salts thereof, it is meant—in the context of chelants—all saltscomprising the same functional structure as the chelant they arereferring to and including alkali metal salts, alkaline earth salts,ammonium salts, substituted ammonium salts, and mixtures thereof;alternatively sodium salts, potassium salts, ammonium salts, andmixtures thereof; alternatively monoethanolammonium salts,diethanolammonium salts, triethanolammonium salts, and mixtures thereofSuitable aminocarboxylic acid chelants comprise at least one carboxylicacid moiety (—COOH) and at least one nitrogen atom. Suitableaminocarboxylic acid chelants include, but are not limited to:diethylenetriamine pentaacetic acid (DTPA), ethylenediamine disuccinicacid (EDDS), ethylenediamine diglutaric acid (EDGA),2-hydroxypropylenediamine disuccinic acid (HPDS),glycinamide-N,N′-disuccinic acid (GADS), ethylenediamine-N-N′-diglutaricacid (EDDG), 2-hydroxypropylenediamine-N-N′-disuccinic acid (HPDDS),ethylenediaminetetraacetic acid (EDTA), ethylenedicysteic acid (EDC),ethylenediamine-N-N′-bis(ortho-hydroxyphenyl acetic acid) (EDDHA), diaminoalkyldi(sulfosuccinic acids) (DDS),N,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid (HBED), theirsalts thereof, and mixtures thereof. Other suitable aminocarboxylic typechelants include, but are not limited to: iminodiacetic acid derivativessuch as N-2-hydroxyethyl N,N diacetic acid or glyceryl imino diaceticacid, iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and asparticacid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid,β-alanine-N,N′-diacetic acid, aspartic acid-N,N-diacetic acid, asparticacid-N-monoacetic acid and iminodisuccinic acid chelants,ethanoldiglycine acid, their salts thereof, their derivatives thereofand mixtures thereof. Further suitable aminocarboxylic type chelantsinclude, but are not limited to: dipicolinic acid,2-phosphonobutane-1,2,4-tricarboxylic acid, their salts thereof, theirderivatives thereof, and mixtures thereof.

Suitable aminophosphonic acid chelants comprise an aminophosphonic acidmoiety (—PO3H2) or its derivative—PO3R2, wherein R₂ is a C₁ to C₆ alkylor aryl radical and salts thereof. Suitable aminophosphonic acidchelants include, but are not limited to: aminotri-(1-ethylphosphonicacid), ethylene-diaminetetra-(1-ethylphosphonic acid),aminotri-e-propylphosphonic acid), aminotri-(isopropylphosphonic acid),their salts thereof and mixtures thereof alternativelyaminotri-(methylenephosphonic acid),ethylene-diamine-tetra-(methylenephosphonic acid) (EDTMP) anddiethylene-triamine-penta-(methylenephosphonic acid) (DTPMP), theirsalts thereof, their derivatives thereof, and mixtures thereof.

Suitable alternative chelants include, but are not limited to:polyethyleneimines, polyphosphoric acid chelants, etidronic acid,methylglycine diacetic acid, N-(2-hydroxyethyl)iminodiacetic acid,minodisuccinnic acid, N,N-Dicarboxymethyl-L-glutamic acid,N-lauroyl-N,N′,N″-ethylenediamine diacetic acid, their salts thereof,their derivatives thereof, and mixtures thereof.

In a specific embodiment, the composition comprises a chel.ant selectedfrom the group consisting of diethylenetriamine-N,N′,N″-polyacids,diethylenetriaminepentaacetic acid (DTPA),diethylenetriaminepenta(methylene phosphonic acid) (DTPMP),diamine-N,N′-dipolyacid, monoamine monoamide-N,N′-dipolyacid,ethylenediaminedisuccinic acid (EDDS), their salts thereof theirderivatives thereof, and mixtures thereof alternativelyethylenediaminedisuccinic acid (EDDS).

When the hair color composition is obtained by mixing a tint compositionand a developer composition, the chelants may be incorporated in thetint composition and/or in the developer composition. A chel ant may bepresent in the developer composition for stability.

Radical Scavengers

The hair color compositions described herein may comprise a radicalscavenger. As used herein the term radical scavenger refers to a speciesthat can react with a radical, to convert the radical species by aseries of fast reactions to an unreactive or less reactive species. Theradical scavenger is also preferably selected such that it is not anidentical species as the alkalising agent and is present in an amountsufficient to reduce the damage to the hair during thecolouring/bleaching process. The compositions of the present inventioncomprise a radical scavenger from about 0.1% to about 10%, preferablyfrom about 1% to about 7% by weight of the radical scavenger relative tothe total weight of the composition.

Suitable radical scavengers for use herein may be selected from theclasses of alkanolamines, amino sugars, amino acids, esters of aminoacids and mixtures thereof Suitable compounds include3-substituted-pyrazol-5-ones, 3-carboxy-1H-pyrazol-5-one,3-methyl-1-phenyl-pyrazol-5-one, 3-methyl-1-p-tolyl-pyrazol-5-one,3-methyl-1-(4-sulfophenyl)-pyrazol-5-one,3-methyl-1-(4-sulfoamidophenyl)-pyrazol-5-one,3-methyl-1-(3-sulfophenyl)-pyrazol-5-one,3-methyl-1-(3-sulfoamidophenyl)-pyrazol-5-one,3-methyl-1-(2-chloro-5-sulfophenyl)-pyrazol-5-one,3-methyl-1-(2,5-dichloro-4-sulfophenyl)-pyrazol-5-one,3-methyl-1-(4-chlorophenyl)-pyrazol-5-one,3-methyl-1-(4-carboxyphenyl)-pyrazol-5-one,3-carboxy-1-phenyl-pyrazol-5-one,3-carboxy-1-(4-sulfophenyl)-pyrazol-5-one, 3-diphenyl-pyrazol-5-one,methyl pyrazol-5-one-3-carboxylate, 3-amino-1-propanol,4-amino-1-butanol,5-amino-1-pentanol, 1-amino-2-propanol,1-amino-2-butanol, 1-amino-2-pentanol, 1-amino-3-pentanol,1-amino-4-pentanol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine,N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine,histidine, sarcosine, serine, glutamic acid, tryptophan, or mixturesthereof, or the salts, such as the potassium, sodium, or ammonium saltsthereof, or mixtures thereof. In some embodiments, the inventivecompositions may comprise glycine, sarcosine, lysine, serine,2-methoxyethylamine, glucosamine, glutamic acid, morpholine, piperidine,ethylamine, 3-amino-1-propanol, or mixtures thereof.

pH Modifiers and Buffering Agents

The hair color compositions described herein may further comprise, inaddition to the alkalizing agent discussed above, a pH modifier and/orbuffering agent in an amount that is sufficiently effective to adjustthe pH of the composition to fall within a range from about 3 to about13, alternatively from about 8 to about 12, alternatively from about 9to about 11.

Suitable pH modifiers and/or buffering agents include, but are notlimited to: ammonia; alkanolamides (such as monoethanolamine,diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,tripropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol,2-amino-2-hydroxymethyl-1,3,-propandiol); guanidium salts; alkali metaland ammonium hydroxides and carbonates; and mixtures thereof.

Further pH modifiers and/or buffering agents include, but are notlimited to: sodium hydroxide; ammonium carbonate; acidulents (such asinorganic and inorganic acids including for example phosphoric acid,acetic acid, ascorbic acid, citric acid or tartaric acid, hydrochloricacid); and mixtures thereof.

Thickeners and/or Rheology Modifiers

The hair color compositions described herein may further comprise athickener in an amount sufficient to provide the composition with aviscosity so that it can be readily applied to the hair without undulydripping off the hair and causing mess.

In an embodiment, the hair color compositions may comprise a totalamount of thickeners ranging from at least about 0.1%, alternatively atleast about 1%, alternatively at least about 10%, alternatively at leastabout 20%, by weight of the total composition.

Suitable thickeners include, but are not limited to: associativepolymers, polysaccharides, non-associative polycarboxylic polymers, andmixtures thereof.

As used herein, the expression “associative polymers” means amphiphilicpolymers comprising both hydrophilic units and hydrophobic units, forexample, at least one C8 to C30 fatty chain and at least one hydrophilicunit. Associative polymers are capable of reversibly combining with eachother or with other molecules. Suitable associative thickeners include,but are not limited to: nonionic amphiphilic polymers comprising atleast one hydrophilic unit and at least one fatty-chain unit; anionicamphiphilic polymers comprising at least one hydrophilic unit and atleast one fatty-chain unit; cationic amphiphilic polymers comprising atleast one hydrophilic unit and at least one fatty-chain unit; andamphoteric amphiphilic polymers comprising at least one hydrophilic unitand at least one fatty-chain unit, and mixtures thereof.

Suitable nonionic amphiphilic polymers comprising at least one fattychain and at least one hydrophilic unit include, but are not limited to:celluloses modified with groups comprising at least one fatty chain(such as hydroxyethylcelluloses modified with groups comprising at leastone fatty chain chosen from alkyl, alkenyl and alkylaryl groups);hydroxypropyl guars modified with groups comprising at least one fattychain; polyether urethanes comprising at least one fatty chain (such asC8-C30 alkyl or alkenyl groups); copolymers of vinylpyrrolidone and offatty-chain hydrophobic monomers; copolymers of C1-C6 alkyl acrylates ormethacrylates and of amphiphilic monomers comprising at least one fattychain; copolymers of hydrophilic acrylates or methacrylates and ofhydrophobic monomers comprising at least one fatty chain, and mixturesthereof. Commercially available anionic materials include those sold asSepigel 305 by Seppic.

Suitable nonionic amphiphilic polymers comprising at least onehydrophilic unit and at least one fatty-chain unit include, but are notlimited to: those polymers comprising at least one fatty-chain allylether unit and at least one hydrophilic unit comprising an ethylenicunsaturated anionic monomeric unit (such as a vinylcarboxylic acid unit,particularly a unit chosen from units derived from acrylic acids,methacrylic acids, and mixtures thereof), wherein the fatty-chain allylether unit corresponds to the monomer of formula (XV) below

CH2=C(R1)CH2OBnR 6  (XV)

in which R1 is chosen from H and CH3, B is an ethyleneoxy radical, n ischosen from zero and integers ranging from 1 to 100, R is chosen fromhydrocarbon-based radicals chosen from alkyl, alkenyl, arylalkyl, aryl,alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms,and, further, for example, from 10 to 24 carbon atoms and even further,for example, from 12 to 18 carbon atoms.

Suitable anionic amphiphilic polymers include, but are not limited to:those polymers comprising at least one hydrophilic unit of unsaturatedolefinic carboxylic acid type, and at least one hydrophobic unit of thetype such as a (C8-C30) alkyl ester or (C8-C30) oxyethylenated alkylester of an unsaturated carboxylic acid, wherein the hydrophilic unit ofunsaturated olefinic carboxylic acid type corresponds to, for example,the monomer of formula (XVI) below

CH2=C(R1)COOH   (XVI)

in which R1 is chosen from H, CH3, C2H5 and CH2COOH (i.e. acrylic acid,methacrylic, ethacrylic and itaconic acid units); and wherein thehydrophobic unit of the type such as a (C8-C30) alkyl ester or (C8-C30)oxyethylenated alkyl ester of an unsaturated carboxylic acid correspondsto, for example, the monomer of formula (XVII) below

CH2=C(R1)COOBnR2   (XVII)

in which R1 is chosen from H, CH3, C2H5 and CH2COOH (i.e. acrylate,methacrylate ethacrylate and itaconate units), B is an ethyleneoxyradical, n is chosen from zero and integers ranging from 1 to 100. R2 ischosen from C8-C30 alkyl radicals, for example, C12-C22 alkyl radical.Anionic amphiphilic polymers may further be cross-linked. Thecrosslinking agent can be a monomer comprising a group (XVIII) below

CH2═C<  (XVIII)

with at least one other polymerizable group whose unsaturated bonds arenot conjugated with respect to one another. Mention may be made, forexample, of polyallyl ethers such as polyallylsucrose and polyallylpentaerythritol.

Suitable cationic amphiphilic polymers include, but are not limited to:quaternized cellulose derivatives and polyacrylates comprising aminoside groups. The quaternized cellulose derivatives are, for example,chosen from quaternized celluloses modified with groups comprising atleast one fatty chain, such as alkyl, arylalkyl and alkylaryl groupscomprising at least 8 carbon atoms, and mixtures thereof, quaternizedhydroxyethylcelluloses modified with groups comprising at least onefatty chain, such as alkyl, arylalkyl and alkylaryl groups comprising atleast 8 carbon atoms, and mixtures thereof The alkyl radicals borne bythe above quaternized celluloses and hydroxyethylcelluloses, forexample, contain from 8 to 30 carbon atoms. The aryl radicals, forexample, are chosen from phenyl, benzyl, naphthyl and anthryl groups.

Suitable amphoteric amphiphilic polymers comprising at least onehydrophilic unit and at least one fatty-chain unit, may be made, forexample, of methacrylamidopropyltrimethylammonium chloride/acrylicacid/C8-C30 alkyl methacrylate copolymers, wherein the alkyl radical is,for example, a stearyl radical.

In an embodiment, the associative polymers may comprise at least onehydrophilic unit which is unsaturated carboxylic acid or itsderivatives, and at least one hydrophobic unit which is a C8 to C30alkyl ester or oxyethylenated C8-C30 alkyl ester of unsaturatedcarboxylic acid. The unsaturated carboxylic acid is preferably acrylicacid, methacrylic acid or itaconic acid. Commercially availablematerials include those sold as Aculyn-22 by Rohm & Haas; Permulen TRI,Carbopol 2020, Carbopol Ultrez-21/−30 by Noveon, Structure 2001/3001 byNational Starch. Other preferred associative polymers include polyetherpolyurethane, commercially available as Aculyn-44/−46 by Rohm and Haas.Further preferred associative polymers include cellulose modified withgroups comprising at least one C8 -C30 fatty chain, commerciallyavailable under the trade name Natrosol Plus Grade 330 CS by Aqualon.

Suitable non-associative cross-linked polycarboxylic polymers include,but are not limited to: cross-linked acrylic acid homopolymers,copolymers of acrylic or (meth)acrylic acid and of Ci-C6 alkyl acrylateor (meth)acrylate, and mixtures thereof. Commercially availablematerials include those sold as Carbopol 980/981/954/1382/2984/5984 byNoveon, Synthalen M/Synthalen L/Synthalen K/Synthalen CR by 3V,Aculyn-33 by Rohm and Haas.

Suitable polysaccharides include, but are not limited to: glucans,modified and unmodified starches (such as those derived, for example,from cereals, for instance wheat, corn or rice, from vegetables, forinstance yellow pea, and tubers, for instance potato or cassaya),amylose, amylopectin, glycogen, dextrans, celluloses and derivativesthereof (methyiceliuloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, and carboxymethylcelluloses), mannans, xylans,lignins, arabans, galactans, galacturonans, chitin, chitosans,glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acidsand pectins, alginic acid and alginates, arabinogalactans, carrageenans,agars, glycosaminoglucans, gum arabics, gum tragacanths, ghatti gums,karaya gums, carob gums, galactomannans, such as guar gums, and nonionicderivatives thereof (hydroxypropyl guar) and bio-polysaccharides, suchas xanthan gums, gellan gums, welan gums, scleroglucans, succinoglycans,and mixtures thereof. Suitable polysaccharides are described in“Encyclopedia of Chemical Technology”, Kirk-Othmer, Third Edition, 1982,volume 3, pp. 896-900, and volume 15, pp. 439-458, in “Polymers inNature” by E. A. MacGregor and C. T. Greenwood, published by John Wiley& Sons, Chapter 6, pp. 240-328,1980, and in “IndustrialGums—Polysaccharides and their Derivatives”, edited by Roy L. Whistler,Second Edition, published by Academic

Press Inc., all three being incorporated herein by reference. Apreferred polysaccharide is a bio-polysaccharide, particularlybio-polysaccharides selected from xanthan gum, gellan gum, welan gum,scieroglucan or succinoglycan; commercially available as Keltrol® T byKelco and Rheozan® by Rhodia Chimie. Another preferred polysaccharide ishydroxypropyl starch derivative, particularly hydroxypropyl starchphosphate, commercially available as Structure XL® by National Starch, ahydrophobically modified cellulose derivative, commercially available asStructure® Cel 500 HM by AkzoNobel.

Commercially available salt-tolerant thickeners include, but not limitedto: xanthan, guar, hydroxypropyl guar, scleroglucan, methyl cellulose,ethyl cellulose (commercially available as Aquacote), hydroxyethylcellulose (Natrosol), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (Klucel), hydroxyethyl ethyl cellulose, cetylhydroxyethyl cellulose (Natrosol Pius 330), polyvinylpyrrolidone(Povidone, FlexiThix™), Acrylates/Ceteth-20 Itaconate Copolymer(Structure 3001), hydroxypropyl starch phosphate (Structure ZEA),polyethoxylated urethanes or polycarbamyl polyglycol ester such asPEG-150/Decyl/SMDI copolymer (Aculyn 44), PEG-150/Steary1/SMDI copolymer(Aculyn 46), trihydroxystearin (Thixcin), acrylates copolymer (Aculyn33) or hydrophobically modified acrylate copolymers (such asAcrylates/Steareth-20 Methacrylate Copolymer as Aculyn 22),acrylates/steareth-20 methacrylate crosspolymer (Aculyn 88),acrylates/vinyl neodecanoate crosspolymer (Aculyn 38),acrylates/beheneth-25 methacrylate copolymer (Aculyn 28),acrylates/C10-30 alkyl acrylate crosspolymer (Carbopol ETD 2020),non-ionic amphophilic polymers comprising at least one fatty chain andat least one hydrophilic unit selected from polyether urethanescomprising at least one fatty chain, blends of Ceteth—10 phosphate,Dicetyl phosphate and Cetearyl alcohol (available as Crodafos CES), andmixtures thereof.

Salt

In an embodiment, cosmetically acceptable salt, such as ammonium, sodiumor potassium salts with appropriate counter ions, may be added to thehair color compositions described herein to act as leveling agents tominimize patchy coloring results.

Carbonate Ion Sources

The hair color compositions described herein may further comprise asource of carbonate ions, carbamate ions, hydrogen carbonate ions, andmixtures thereof in a sufficient amount to reduce damage to the hairduring the coloring process.

In an embodiment, the hair color compositions may comprise a totalamount of a carbonate ion source ranging from about 0.1% to about 15%,alternatively from about 0.1% to about 10%, alternatively from about 1%to about 7%, by weight of the total composition.

Suitable carbonate ion sources include, but are not limited to: sodiumcarbonate, sodium hydrogen carbonate, potassium carbonate, potassiumhydrogen carbonate, guanidine carbonate, guanidine hydrogen carbonate,lithium carbonate, calcium carbonate, magnesium carbonate, bariumcarbonate, ammonium carbonate, ammonium hydrogen carbonate and mixturesthereof; alternatively sodium hydrogen carbonate, potassium hydrogencarbonate, and mixtures thereof alternatively ammonium carbonate,ammonium hydrogen carbonate, and mixtures thereof.

Conditioning Agents

The hair color compositions described herein may further comprise aconditioning agent, and/or be used in combination with a compositioncomprising a conditioning agent.

In an embodiment, the hair color compositions may comprise a totalamount of conditioning agents ranging from about 0.05% to about 20%,alternatively from about 0.1% to about 15%, alternatively from about0.2% to about 10%, alternatively from about 0.2% to about 2%,alternatively from about 0.5% to 2%, by weight of the total composition.The conditioning agent may be included in a separate pre-and/orpost-treatment composition.

Suitable conditioning agents include, but are not limited to: silicones,aminosilicones, fatty alcohols, polymeric resins, polyol carboxylic acidesters, cationic polymers, cationic surfactants, insoluble oils and oilderived materials and mixtures thereof. Additional conditioning agentsinclude mineral oils and other oils such as glycerin and sorbitol.

Particularly useful conditioning materials may be cationic polymers.Conditioners of cationic polymer type can be chosen from thosecomprising units of at least one amine group chosen from primary,secondary, tertiary and quaternary amine groups that may either formpart of the main polymer chain, or be borne by a side substituent thatis directly attached to the main polymer chain, described hereinafter.

Suitable silicones include, but are not limited to: polyalkylsiloxaneoils, linear polydimethylsiloxa.ne oils containing trimethylsilyl orhydroxydimethylsiloxane endgroups, polymethylphenylsiloxane,polydimethylphenylsiloxane or polydimethyldiphenylsiloxane oils,silicone resins, organofunctional siloxanes having in their generalstructure one or a number of organofunctional group(s), the same ordifferent, attached directly to the siloxane chain and mixtures thereof.Said organofunctional group(s) may be selected from: polyethyleneoxyand/or polypropyleneoxy groups, (per)fluorinated groups, thiol groups,substituted or unsubstituted amino groups, carboxylate groups,hydroxylated groups, alkoxylated groups, quaternium ammonium groups,amphoteric and betaine groups. The silicone can either be used as a neatfluid or in the form of a pre-formed emulsion. Suitable silicones alsoinclude: silicones containing groups that may be ionized into cationicgroups, for example aminosilicones containing at least 10 repeatingsiloxane (Si(CH₃)₂—O) units within the polymer chain, with eitherterminal, graft, or a mixture of terminal and graft aminofunctionalgroups. Example functional groups are not limited toaminoethylaminopropyl, aminoethylaminoisobutly, aminopropyl. In the caseof graft polymers, the terminal siloxane units can be (CH₃)₃Si—O,R₁₂(CH₃)₂Si—O, where R₁₂₅ can be either OH or OR₁₃, where R₁₃ is a C1-C8alkyl group, or a mixture of both terminal groups. These silicones arealso available as prethimed emulsions. Commercially availableaminosilicones include those sold as DC-2-8566, DC 7224, DC-2-8220 byDow Corning; SF1708, SM2125 by GE Silicones; Wacker Belsil ADM 653/ADM1100/ADM 1600/ADM 652/ADM 6057E/ADM 8020 by Wacker Silicones; DC929,DC939, DC949 by Dow Corning; SM2059 by GE Silicones. Suitableaminosilicones may also contain additional functional groups,particularly additional functional groups including polyoxyalkylene, thereaction product of amines and carbinols, and alky chains. Commerciallyavailable materials are known as methoxy PEG/PPG-7/3 AminopropylDimethicone (e.g. Abil Soft AF100, by Degussa), or as Bis(C13-15Alkoxy)PG Amodimethicone (e.g. DC 8500, by Dow Corning).

Suitable cationic polymers include, but are not limited to: polymerscomprising units of at least one amine group chosen from primary,secondary, tertiary and quaternary amine groups that may either formpart of the main polymer chain or be borne by a side substituent that isdirectly attached to the main polymer chain. Such cationic polymersgenerally have a number average molecular mass ranging from about 500 toabout 5×10⁶, alternatively from about 1000 to about 3×10⁶. Preferablythe cationic polymers are selected from polymers of the polyamine,polyamino amide and polyquaternary ammonium type.

Suitable polymers of the polyamine, polyamino amide and polyquaternaryammonium type include, but are not limited to:

1) Homopolymers and copolymers derived from acrylic or methacrylicesters or amides. Copolymers of these polymers may also comprise atleast one unit derived from comonomers which may be chosen from thefamily of acrylamides, methacrylamides, diacetone acylamides,acrylamides and methacrylicamides substituted on the nitrogen with atleast one group chosen from lower (C1-C4) alkyls, acrylic andmethacrylic acids and esters thereof, vinlylactams such asvinlypyrrolidone and vinylcaprolactam, and vinyl esters. Suitableexamples include copolymers of acrylamide and ofmethacryloyloxyethyltrimethylammonium methosulfate, including polymersknown as Polyquaternium-5 (e.g. commercially available under the tradename Reten 210/220/230/240/1104/1105/1006 by Hercules; Merquat 5/5 SF byNalco); copolymers of vinylpyrrolidone and dimethylaminopropylmethacrylamide, including polymers known as Polyquatemium-28 (e.g.Gafquat HS-100 by ISP); coplolymers of vinyl pyrrolidone anddialkyaminoalkyl acrylates or methactylates, including polymers known asPolquaternium-11 (see Gafquat 440/734/755/755N by ISP; Luviquat PQ11 PMby BASF; Polyquat-11 SL by Sino Lion); copolymers vinylpyrrolidone,dimethylaminopropyl methacrylamide and methacryloylaminopropyllauryldimonium chloride, including polymers known as polyquaternium-55(e.g. Styleze W-20 by ISP); copolymers of acrylic acid, acrylamide andmethacrylamidopropyltrimonium chloride, including polymers known asPolyquaternium-53 (e.g. Merquat 2003 by Nalco); copolymers ofdimethyaminopropylacrylate (DMAPA), acrylic acid and acrylonitrogens anddiethyl sulphate, including polymers known as Polyquaternium-31 (e.g.Hypan QT100 by Lipo); copolymers of acrylamide,acrylamidopropyltrimonium chloride, 2-amidopropylacrylamide sulfonate,and dimethyaminopropylacrylate (DMAPA), including polymers known aspolyquatemium-43 (e.g. Bozequat 4000 by Clairant); copolymers of acrylicacid, methylacrylate and methacrylamidopropyltrimonium chloride,including polymers known as Polyquaternium-47 (e.g. Merquat 2001/2001Nby Nalco); copolymers of methacryloyl ethyl betaine, 2-hydroxyethylmethacrylate and methacryloyl ethyl trimethyl ammonium chloride,including polymers known as Polyquaternium-48 (e.g. Plascize L-450 byGoo Chemical); copolymers of acrylic acid diallyl dimethyl ammoniumchloride and acrylamide, including polymers known as polyquaternium-39(e.g. Merquat 3330/3331 by Nalco). Further suitable examples includecopolymers of methacrylamide methacrylamido-propyltrimonium andmethacryloylethyltrimethyl ammonium chloride and their derivatives,either homo or copolymerised with other monomers, including polymersknown as Polyquaternium-8, Polyquaternium-9, Polyquaternium-12,Polyquaternium-13 Polyquaternium-14, Polyquaternium-15 (e.g. Rohagit KF720 F by Rohm), Polyquaternium-30 (e.g. Mexomere PX by Chimex),Polyquaternium-33, Polyquaternium-35, Polyquaternium-36 (e.g. Plex 3074L by Rhon), Polyquaternium 45 (e.g. Plex 3073L by Rohn), Polyquaternium49 (e.g. Plascize L-440 by Goo Chemicals), Polyquaternium 50 (e.g.Pla.scize L-441 by Goo Chemicals), Polyquaternium-52.

2) Cationic polysaccharides, such as cationic celluloses and cationicgalactomannan gums. Among the cationic polysaccharides that maybementioned, for example, are cellulose ether derivatives comprisingquaternary ammonium groups and cationic cellulose copolymers orcellulose derivatives grafted with a water-soluble quaternary ammoniummonomer and cationic galactomannan gums. Suitable examples includecopolymers of hydroxyethylcelluloses and diallyldimethyl ammoniumchlorides, including polymers known as Polyquaternium-4 (e.g. Celquat L200 and Celquat H 100 by National Starch); copolymers ofhydroxyethylcelluloses and a trimethyl ammonium substituted epoxide,including polymers known as Polyquaternium-10 (e.g. AEC Polyquatemium-10by A&E Connock; Catinal C-100/HC-35/HC-100/HC-200/LC-100/LC-200 by Toho;Celquat SC-240C/SC-230M by National Starch; Dekaquat 400/3000 by Dekker;Leogard GP by Akzo Nobel; RITA Polyquat 400/3000 by RITA; UCARE PolymerJR-125/JR-400/JR-30M/LK/LR 400/LR 30M by Amerchol); copolymers ofhydroxyethylcelluloses and lauryl dimethyl ammonium substitutedepoxides, including polymers known as Polyquatemium-24 (es. Quatrisoftpolymer LM-200 by Amerchol); derivatives of hydroxypropyl guar,including polymers as guar hydroxypropyltrimonium chloride (e.g. CatinalCG-100, Catinal CG-200 by Toho; Cosmedia Guar C-261N, Cosmedia GuarC-261N, Cosmedia. Guar C-261N by Cognis; DiaGum P 5070 by FreedomChemical Diamalt; N-Hance Cationic Guar by Hercules/Aqualon; Hi-Care1000, Jaguar C-17, Jaguar C-2000, Jaguar C-13S, Jaguar C-14S, JaguarExcel by Rhodia; Kiprogum CW, Kiprogum NGK. by Nippon Starch);hydroxypropyl derivatives of guar hydroxypropyltrimonium chloride,including polymers known as hydroxypropyl guar hydroxypropyltrimoniumchloride (e.g. Jaguar C-162 by Rhodia).

3) Polyamino amide derivatives resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationwith difunctional agents. Among the derivative, mention may be made forexample to adipic acid/dimethylaminohydroxypropyl/diethylenetriamine.

4) Polymers obtained by reaction of a polyalkylene polyamine comprisingtwo primary amines groups and at last one secondary amine group with adecarboxylic acid chosen from diglycolic acids and saturated aliphaticdicarboxylic acids comprising from 3 to 8 carbon atoms. Suitableexamples include the polymer adipic acid/epxoypropyl/diethylenetriamine.

5) Cyclopolymers of dialkdiallylamine or of dialkyldiallyammonium,including: Dimethyldiallyammonium chloride polymers, including polymersknown as Polyquaternium-6 (e.g. Merquat 100 by Nalco; Mirapol 100 byRhodia; Rheocare CC6 by Cosmetic Rheologies; AFC polyquaternium-6 by A&EConnock; Agequat 400 by CPS; Conditioner P6 by 3V Inc.; Flocare C106 bySNF; Genamin PDAC by Clariant; Mackernium 006 by McIntyre); copolymersof acrylamides and dimethyldiallylammonium chlorides monomers, includingpolymers known as Polyquatemium-7 (e.g. AFC Polyquaternium-7 by A&EConnock; Agequat-5008/C-505 by CPS; Conditioner P7 by 3V :Inc.; FlocareC 107 by SNF; Mackemium 007/007S by McIntyre; ME Polymer 09W by Toho;Merquat 550/2200/S by Nalco; Mirapol 550 by Rhodia; Rheocare CC7/CCP7 byCosmetic Rheologies; Salcare HSP-7/SC10/ Super 7 by Ciba); copolymers ofdimethyldiallylammoniumchlorides and acrylic acids, including polymersknown as polyquaternary-22 (e.g. Merquat 280/Merquat 295 by Nalco).

6) Quaternary diammonium polymers comprising repeat units correspondingto [—N+(R1)(R2)—Al—N+(R3)(R4)-Bl—] [2X—], in which R1, R2, R3 and R4,which may be identical or different, are chosen from aliphatic,alicyclic and arylaliphatic radicals comprising from 1 to 20 carbonatoms and from lower hydroxyalkylaliphatic radicals, or R1, R2, R3 andR4, together or separately, constitute, with the nitrogen atoms to whichthey are attached, heterocycles optionally comprising a secondheteroatom other then nitrogen, or R1, R2, R3 and R4, are chosen fromliner or branched C1-C6 alkyl radicals substituted with at least onegroup chosen from nitrile, ester, acyl and amide groups and groups of—CO—O—R5-D and —CO—NH—R5-D wherein R5 is chosen from alkylene groups andD is chosen from quaternary ammonium groups. A1 and B1, which may beidentical or different, are chosen from linear and branched, saturatedor unsaturated polymethylene groups comprising 2 to 20 carbon atoms. Thepolymethylene groups may comprise, linked to or intercalated in the mainring, at least one entity chosen from aromatic rings, oxygen and sulphuratoms and sulphoxide, sulphone, disulphide, amino, alkylamino, hydroxyl,quaternary, ammonium, ureido, amide and ester groups, and X— is an anionderived from inorganic and organic acids. D is chosen from a glycolresidue, a bis-secondary diamine residue, a bis-primary diamine residueor a ureylene group. Suitable examples include polymers known asHexadimethrine chloride, where R1, R2, R3 and R4 are each methylradicals, A1 is (CH2)3 and B1 is (CH2)6 and X═Cl; as polyquaternium-34where R1 and R2 are ethyl radicals and R3 and R4 are methyl radicals andA1 is (CH2)3 and B1 is (CH2)3 and X═Br (e.g. Mexomere PAX by Chimax). 7)Polyquaternary ammonium polymers comprising repeating units of formula[—N+(R6)(R7)-(CH2)r-NH—CO-(CH2)q-(CO)t-NH—(CH2)s-N+(R8)(R9)—A—][2X—], inwhich R6, R7, R8 and R9 which may be identical or different, are chosenfrom a hydrogen atom and a methyl, ethyl, propyl, hydroxyethyl,hydroxypropyl, and —CH2CH2(OCH2CH2)pOH radicals, wherein p is equal to 0or an integer ranging from 1 to 6, wherein R6, R7, R8 and R9 do not allsimultaneously represent a hydrogen atom. R and s which maybe identicalor different are each an integer ranging from 1 to 6, q is equal to 0 oran integer ranging from 1 to 34 and X— is anion such as a halide. T isan integer chosen to be equal to 0 or 1. A is chosen from divalentradicals such as —CH2—CH2—O—CH2—H2—. Suitable examples include: polymersknown as polyquaternium-2, where r=s=3, q=0,t=0, R6, R7, R8 and R9 aremethyl groups, and A is —CH2—CH2—O—CH2—CH2 (e.g. Ethpol PQ-2 from Ethox;Mirapol A-15 by Rhodia); as polyquaternium-17 where r=s=3, q=4, t=l R6,R7, R8 and R9 are methyl groups, and A is —CH2—CH2—O—CH2—CH2; asPolyquaternium 18, where r=s=3, q=7, t=l R6, R7, R8 and R9 are methylgroups, and A is —CH2—CH2—O—CH2—CH2; as the block copolymer formed bythe reaction of Polyquatemium-2 with Polyquaternium-17, which are knownas Polyquaternium 27 (e.g. Mirapol 175 by Rhodia).

8) Copolymers of vinylpyrrolidones and of vinylimidazoles and optionallyvinylcaprolactums, including polymers known as Polyquaternary-16 formedfrom methylvinylimidazolium chlorides and vinylpyrrolidones (e.g.Luviquat FC370//FC550/FC905/HM-552 by BASF); copolymers ofvinylcaprolactams and vinylpyrrolidones with methylvinylimidazoliummethosulfates, including polymers known as Polyquaternium-46 (e.g.Luviquat Hold by BASF); copolymers of vinylpyrrolidones and quatemizedimidazolines, including polymers known as polyquaternary 44 (e.g.Luviquat Care by BASF).

9) Polyamines such as Polyquart H sold by Cognis under the referencename polyethylene glycol (15) tallow polyamine.

10) Cross linked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium saltpolymers such as the polymers obtained by homopolymerisation ofdimethylaminoethyl methacrylates quatemized with methyl chloride, or bycopolymerisation of acrylamides with dimethylaminoethyl methacrylatesquaternized with methyl chloride, the homo or copolymerisation beingfollowed by crosslinking with a compound comprising olefinicunsaturation, such as methylenebisacrylamides, including polymers knownas Polyquatemium-37 (e.g. Synthalen CN/CR/CU sold by 3V sigma; or as adispersion in another media such as Salcare SC95/SC96 by Ciba; RheocareCTH(E) by Cosmetic Rheologies) and polymers known as Polyquaternium-32(e.g. sold as a dispersion in mineral oil such as Salcare SC92 by Ciba).

11) Further examples of cationic polymers include polymers known asPolyquaternium 51 (e.g. Lipidure-PMB by NOF), as Polyquaternium 54 (e.g.Qualty-Hy by Mitsui), as Polyquaternium 56 (e.g. Hairrol UC-4 by Sanyochemicals), as Polyquaternium 87 (e.g. Luviquat sensation by BASF).

12) Silicone polymers comprising cationic groups and/or groups which maybe ionised into cationic groups. Suitable examples include cationicsilicones of the general formula(R10-N+(CH3)2)-R11-(Si(CH3)2-O)x-R11-(N+(CH3)2)-R10), where R10 is analkyl. derived from coconut oil, and R11 is (CH2CHOCH2O(CH2)3 and x is anumber between 20 and 2000, including polymers known as Quatemium 80(e.g. Abil Quat 3272/3474 sold by Goldschmidt); silicones containinggroups which may be ionised into cationic groups, for exampleaminosilicones containing at least 10 repeating siloxane -(Si(CH3)2-O)units within the polymer chain, with either terminal, graft or a mixtureof terminal and graft aminofunctional groups. Example functional groupsare not limited to aminoethylaminopropyl, aminoethylaminoisobutly,aminopropyl In the case of graft polymers, the terminal siloxane unitscan either be (CH3)3Si—O or R12(CH3)2Si—O, where R12 can be either OH orOR13, where R13 is a C1-C8 alky group, or a mixture of both functionalterminal groups. These silicones are also available as preformedemulsions. Polymer with terminal siloxane units of (CH3)3Si—O examplesincludes polymers known as trimethylsilylamodimethicone (e.g. DC-2-8566,DC 7224, DC-2-8220 by Dow Coming; SF1708, SM 2125 GE Silicones; WackerBelsil ADM 653 by Wacker silicones). Further examples include polymerswith terminal siloxane units of (R120)(CH3)2Si—O where R12 can be eitherOH or OR13, where R13 is a C 1-C8 alky group, or a mixture of bothfunctional terminal groups, known as amodimethicone (e.g. Wacker BelsilADM 1100/ADM 1600/ADM 652/ADM 6057E/ADM 8020 by Wacker Silicones; DC929,DC939, DC949 by Dow Corning; SM2059 by GE silicones). Siliconescontaining groups which may be ionised into cationic groups—for examplesilicones containing at least 10 repeating siloxane —(Si(CH3)2-O) unitswithin the polymer chain, with either terminal, graft or a mixture ofterminal and graft aminofunctional groups, together with additionalfunctional groups. Additional functional groups can includepolyoxyalkylene, the reaction product of amines and carbinols, alkychains. For example products known as methoxy PEG/PPG-7/3 AminopropylDimethicone (e.g. Abil Soft AF100 by Degussa). For example productsknown as Bis (C13-15 Alkoxy) PG Amodimethicone (e.g. DC 8500 by DowCorning).

In an embodiment, the cationic polymer is selected from the groupconsisting of polyquaternium 37, polyquaternium 7, polyquaternium 22,polyquaternium 87, and mixtures thereof; alternatively from the groupconsisting of polyquaternium 37, polyquaternium 22, and mixturesthereof.

Surfactants

The hair color compositions described herein may further comprise asurfactant. Suitable surfactants generally have a lipophilic chainlength of from about 8 to about 30 carbon atoms and can be selected fromanionic surfactants, nonionic surfactants, amphoteric surfactants,cationic surfactants, and mixtures thereof.

In an embodiment, the hair color compositions may comprise a totalamount of surfactants ranging from about 0.01% to about 60%,alternatively from about 0.05% to about 30%, alternatively from about0.1% to about 25%, alternatively from about 0.1% to about 20%, by weightof the total composition.

The compositions may comprise a mixture of an anionic surfactant and anamphoteric surfactant with one or more nonionic surfactants. Thecomposition may comprise a total amount of anionic surfactant rangingfrom about 0.01% to about 20%, alternatively from about 0.05% to about15%, alternatively from about 0.1% to about 15%, by weight of the totalcomposition; and a total amount of amphoteric and/or nonioniccomponents, which may range independently from each other from about0.01% to about 15%, alternatively from about 0.05% to about 10%,alternatively from about 0.1% to about 8%, by weight of the totalcomposition.

Suitable anionic surfactants include, but are not limited to: salts(such as alkaline salts, for example, sodium salts, ammonium salts,amine salts, amino alcohol salts and magnesium salts) of the followingcompounds: alkyl sulphates, alkyl ether sulphates, alkylamido ethersulphates, alkylarylpolyether sulphates, monoglyceride sulphates; alkylsulphonates, alkyl phosphates, alkylamide sulphonates, alkylarylsulphonates, a-olefin sulphonates, paraffin sulphonates; alkylsulphosuccinates, alkyl ether sulphosuccinates, alkylamidesulphosuccinates; alkyl sulphosuccinamates; alkyl sulphoacetates; alkylether phosphates; acyl sarcosinates; acyl isethionates; N-acyltaurates;and mixtures thereof. The alkyl or acyl radical of all of these variouscompounds, for example, comprises from 8 to 24 carbon atoms, and thearyl radical, for example, is chosen from phenyl and benzyl groups.Among the anionic surfactants, which can also be used, mention may alsobe made of fatty acid salts such as the salts of oleic, ricinoleic,palmitic and stearic acids, coconut oil acid or hydrogenated coconut oilacid; acyl lactylates in which the acyl radical comprises from 8 to 20carbon atoms. Weakly anionic surfactants can also be used, such asalkyl-D-galactosiduronic acids and their salts, as well aspolyoxyalkylenated (C₆-C₂₄) alkyl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylaryl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylamido ether carboxylic acids and theirsalts, for example, those comprising from 2 to 50 ethylene oxide groups,and mixtures thereof. Anionic derivatives of polysaccharides, forexample carboxyalkyl ether of alkyl polyglucosides, can be also used.

Nonionic surfactants are compounds that are well known (see, forexample, in this respect “Handbook of Surfactants” by M. R. Porter,published by Blackie & Son (Glasgow and London), 1991, pp. 116-178).Suitable non-ionic surfactants include, but are not limited to:polyethoxylated, polypropoxylated and polyglycerolated fatty acids,alkyl phenols, a-diols and alcohols comprising a fatty chain comprising,for example, from 8 to 18 carbon atoms, it being possible for the numberof ethylene oxide or propylene oxide groups to range, for example, from2 to 200 and for the number of glycerol groups to range, for example,from 2 to 30. Mention may also be made of copolymers of ethylene oxideand of propylene oxide, condensates of ethylene oxide and of propyleneoxide with fatty alcohols; polyethoxylated fatty amides preferablyhaving from 2 to 30 mol of ethylene oxide and their momoethanolamine anddiethanolamine derivatives, polyglycerolated fatty amides, for example,comprising on average from 1 to 5, and such as from 1.5 to 4, glycerolgroups; polyethoxylated fatty amines such as those containing from 2 to30 mol of ethylene oxide; oxyethylenated fatty acid esters of sorbitanhaving from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose,fatty acid esters of polyethylene glycol, alkylpolyglycosides,N-alkylglucamine derivatives, amine oxides such as (C₁₀-C₁₄)alkylamineoxides or N-acylaminopropylmorpholine oxides.

Suitable amphoteric surfactants include, but are not limited to:aliphatic secondary and tertiary amine derivatives in which thealiphatic radical is chosen from linear and branched chains comprisingfrom 8 to 22 carbon atoms and comprising at least one water-solubleanionic group (for example carboxylate, sulphonate, sulphate, phosphateor phosphonate); mention may also be made of (C₈-C₂₀)alkylbetaines,sulphobetaines, (C₈-C₂₀)alkylamido(C₁-C₆)alkylbetaines or(C₈-C₂₀)alkylamido(C₁-C₆)alkylsulphobetaines. Among the aminederivatives, mention may be made of the products sold as Miranol, asdescribed, for example, in U.S. Pat. Nos. 2,528,378 and 2,781,354 andhaving the structures of: R₂-CON HCH₂CH₂—N⁻(R₃)(R₄)(CH₂COO^(—)), (XIX)in which: R₂ is chosen from alkyl radicals derived from an acid R₂—COOHpresent in hydrolysed coconut oil, and heptyl, nonyl and undecylradicals, R3 is a β-hydroxyethyl group and R4 is a carboxymethyl group;and of R₅—CONHCH₂CH₂—N(B)(C) (XX) wherein B represents—CH₂CH₂OX′, Crepresents—(CH₂)₂—Y′, with z=1 or 2, X′ is chosen from the —CH₂CH₂—COOHgroup and a hydrogen atom, Y′ is chosen from—COOH and—CH₂—CHOH—SO₃Hradicals, R₅ is chosen from alkyl radicals of an acid R₅—COOH present incoconut oil or in hydrolysed linseed oil, alkyl radicals, such as C₇,C₉, C₁₁ and C₁₃ alkyl radicals, a C₁₁ alkyl radical and its iso form,and unsaturated C₁₇ radical. These compounds are classified in the CTFAdictionary, 5^(th) edition, 1993, under the names disodiumcocoamphodiacetate, disodium lauroamphodiacetate, disodiumcaprylamphodiacetate, disodium capryloamphodiacetate, disodiumcocoamphodipropionate, disodium lauroamphodipropionate, disodiumcaprylamphodipropionate, disodium capryloamphodipropionate,lauroamphodipropionic acid, and cocoamphodipropionic acid. Salts ofdiethyl aminopropyl cocoaspartamid can be also used.

Suitable cationic surfactants include, but are not limited to, thequaternary ammonium salts A) to D) as defined hereinafter:

A) Quaternary ammonium salts of general formula (XXI) below:

wherein X^(—) is an anion chosen from halides (chloride, bromide andiodide), (C₂-C₆)alkyl sulphates, such as methyl sulphate, phosphates,alkyl and alkylaryl sulphonates, and anions derived from organic acids,such as acetate and lactate, and wherein R₁ to R₄ are as below in i) orii).

i) Radicals R₁ to R₃, which may be identical or different, are chosenfrom linear and branched aliphatic radicals comprising from 1 to 4carbon atoms, and aromatic radicals such as aryl and alkylaryl. Thealiphatic radicals may comprise at least one hetero atom such as oxygen,nitrogen, sulphur and halogens. The aliphatic radicals may be chosenfrom: alkyl, alkoxy and alkylamide radicals. R₄ is chosen from linearand branched alkyl radicals comprising from 16 to 30 carbon atoms. Asuitable cationic surfactant is, for example, a.behenyltrimethylammonium salt (for example chloride).

ii) Radicals R₁ and R₂, which may be identical or different, are chosenfrom linear and branched aliphatic radicals comprising from 1 to 4carbon atoms, and aromatic radicals such as aryl and alkylaryl. Thealiphatic radicals may comprise at least one hetero atom such as oxygen,nitrogen, sulphur and halogens. The aliphatic radicals may be chosenfrom alkyl, alkoxy, alkylamide and hydroxyalkyl radicals comprising fromabout 1 to 4 carbon atoms. Radicals R₃ and R₄, which may be identical ordifferent, are chosen from linear and branched alkyl radicals comprisingfrom 12 to 30 carbon atoms, the said alkyl radicals comprise at leastone function chosen from ester and amide functions. R₃ and R₄ may bechosen from (C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl and (C₁₂-C₂₂) alkylacetateradicals. A suitable cationic surfactant is, for example, adicetyldimethyl ammonium salt (for example chloride);

B) Quaternary ammonium salts of imidazolinium of formula (XXII) below:

in which R₅ is chosen from alkenyl and alkyl radicals comprising from 8to 30 carbon atoms, for example fatty acid derivatives of tallow, R₆ ischosen from a hydrogen atom, C₁-C₄ alkyl radicals and alkenyl and alkylradicals comprising from 8 to 30 carbon atoms, R₇ is chosen from C₁-C₄alkyl radicals, R₈ is chosen from a hydrogen atom and C₁-C₄ alkylradicals, and X^(—) is an anion chosen from halides, phosphates,acetates, lactates, alkyl sulphates, alkyl sulphonates and alkylarylsulphonates. In one embodiment, R₅ and R₆ are, for example, a mixture ofradicals chosen from alkenyl and alkyl radicals comprising from 12 to 21carbon atoms, such as fatty acid derivatives of tallow, R₇ is methyl andR₈ is hydrogen. Such a product is, for example, Quatemium-27 (CTFA 1997)or Quaternium-83 (CTFA 1997), commercially available as “Rewoquat®”W75/W90/W75PG/W75HPG by Witco.

C) Diquaternary ammonium salts of formula (XXIII):

in which R₉ is chosen from aliphatic radicals comprising from about 16to 30 carbon atoms, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄, which may be identicalor different, are chosen from hydrogen and alkyl radicals comprisingfrom 1 to 4 carbon atoms, and X^(—) is an anion chosen from halides,acetates, phosphates, nitrates and methyl sulphates. Such diquaternaryammonium salts, for example, include propanetallowdiammonium dichloride.

D) Quaternary ammonium salts comprising at least one ester function, offormula (XXIV) below:

in which: R15 is chosen from C1-C6 alkyl radicals and C1-C6 hydroxyalkyland dihydroxyalkyl radicals; R16 is chosen from: a radical R19C(O)—,linear and branched, saturated and unsaturated C1-C22 hydrocarbon-basedradicals R20, and a hydrogen atom, R18 is chosen from: a radicalR21C(O)—, linear and branched, saturated and unsaturated C1-C6hydrocarbon-based radicals R22, and a hydrogen atom, R17, R19 and R21,which may be identical or different, are chosen from linear andbranched, saturated and unsaturated C7-C21 hydrocarbon-based radicals;n, p and r, which may be identical or different, are chosen fromintegers ranging from 2 to 6; y is chosen from integers ranging from 1to 10; x and z, which may be identical or different, are chosen fromintegers ranging from 0 to 10; X—is an anion chosen from simple andcomplex, organic and inorganic anions; with the proviso that the sumx+y+z is from 1 to 15, that when x is 0, then R16 is R20 and that when zis 0, then R18 is R22. In one embodiment, the ammonium salts of formula(XXXXI) can be used, in which: R15 is chosen from methyl and ethylradicals, x and y are equal to 1; z is equal to 0 or 1; n, p and r areequal to 2; R16 is chosen from: a radical R19C(O)—,methyl, ethyl andC14-C22 hydrocarbon-based radicals, and a hydrogen atom; R17, R19 andR21, which may be identical or different, are chosen from linear andbranched, saturated and unsaturated C7-C21, hydrocarbon-based radicals;R18 is chosen from: a radical R21C(O)— and a hydrogen atom. Suchcompounds are commercially available as Dehyquart by Cognis, Stepanquatby Stepan, Noxamium by Ceca, and Rewoquat WE 18 by Rewo-Witco.

Data

Uptake and washfastness: The uptake total color change (ΔE¹) describeshow much the hair color has changed after white Piedmont hair strandssupplied by International Hair Importers & Products has been dyed. ΔE iscalculated as the square root of sum of squares of ΔL*, Δa* and Δb*. Thetotal color change for washfastness (ΔE²) is measured after the dyedhair switches are processed through a 12-cycle rinse study. One cycle isdefined as two shampoo treatments followed by a conditioning treatment.The hair switches are blow dried between each shampoo treatment. Colordata is collected after the hair is properly dried on a Minoltaspectrophotometer CM-3700d. Examples A and B are commercially availabledirect dye compounds known in the art. Examples C through N areembodiments of the washfast direct dye compounds described herein.

TABLE 1 Washfastness data Name Structure ΔE¹ ΔE² A Vibracolor ® Ruby Red

60 15 B HC Blue 16

76 17 C (E)-2-((4-((2-(bis(2- aminoethyl)amino)ethyl)amino)phenyl)diazenyl)-1,3-dimethyl-1H- imidazol-3-ium trifluoroacetate

61 5 D (E)-3-(4-aminobutyl)-2-((4- (dimethylamino)phenyl)diazenyl)-1-methyl-1H-imidazol-3-ium bromide

61 7 E (E)-3-(3-ammoniopropyl)-2-((4- (dimethylamino)phenyl)diazenyl)-1-methyl-1H-imidazol-3-ium bromide

61 7 F (E)-1,3-bis(3-ammoniopropyl)-2- ((4-(dimethylamino)phenyl)diazenyl)- 1H-imidazol-3-ium bromide

60 5 G (E)-2-((4-aminophenyl)diazenyl)- 1,3-bis(3-ammoniopropyl)-1H-imidazol-3-ium bromide

59 4 H (E)-l,3-bis(3-ammoniopropyl)-2- ((4-(bis(3-ammoniopropyl)amino)phenyl) diazenyl)-1H-imidazol-3-ium chloride

61 5 I (E)-3-(4-ammoniobutyl)-2-((4- ((3- ammoniopropyl)(methyl)amino)phenyl)diazenyl)-1-methyl-1H- imidazol-3-ium bromide

60 5 J (E)-3-(3- (ammoniomethyl)benzyl)-2-((4-(dimethylamino)phenyl)diazenyl)- 1-methyl-1H-imidazol-3-iumtrifluoroacetate

61 7 K (E)-2-((4-(bis(3- aminopropyl)amino)phenyl)diazenyl)-3,4,5-trimethylthiazol- 3-ium methylsulfate

67 6 L (E)-3-(4-aminobutyl)-2-((4- (dimethylamino)phenyl)diazenyl)thiazol-3-ium bromide

62 7 M (E)-4-((2-(5-aminopentyl)-2- phenylhydrazono)methyl)-1-methylpyridin-1-ium iodide

57 6 N (E)-1-(4-aminobutyl)-4-((2-(3- aminopropyl)-2-phenylhydrazono)methyl)pyridin- 1-ium bromide

54 6 ¹uptake on blonde virgin hair ²washfastness on blonde virgin hair

The smaller the total color change (ΔE²) for washfastness after 24shampoos, the more washfast the dye is. Notably, examples C through N,embodiments of the washfast direct dyes described herein, exhibitedsuperior washfastness to examples A and B, commercially available directdye compounds known in the art.

TABLE 2 On-tone fading data on hue angle change for mixed dye systems Δhafter a 12-cycle rinse-blonde Structures Structural Analysis virgin hair

Matching structural construction Both the blue dye and red dye carry onepermanent cation plus one incipient cation. 3.6

Mismatching structural construction. The blue dye carries one permanentcation without additional anchoring group. The red dye carries onepermanent charge plus two incipient cations. 12.0

The smaller the hue angle change (Δh), the better the on-tone fading

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a teon in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A method of dyeing the hair, the method comprising: a. applying tothe hair a hair color composition comprising one or more direct dyecompounds, the one or more direct dye compounds each comprising: i. achromophore; ii. one or two permanent cations, wherein the permanentcations are pendant to the chromophore or part of the chromophore, andwherein the chromophore and the permanent cations form a core structure;and iii. one to four incipient cations, wherein each of the one to fourincipient cations is pendant via a linker group to the core structure,and wherein the incipient cations are neutral; wherein the one or moredirect dye compounds enter the hair shaft after the hair colorcomposition is applied to the hair; and wherein the hair colorcomposition has a pH of from about 7 to about 11; b. rinsing the hairwith water; wherein the pH of the hair after rinsing is from about 3.5to about 6; and wherein the rinsing of the hair causes one or more ofthe one to four incipient cations to change from neutral to positivelycharged inside of the hair shaft, and wherein the chromophore has astructure according to Formula (Xa), Formula (Xc), Formula (Xd), Formula(Xf), Formula (Xg), Formula (Xi), and Formula (Xj), homologs thereof,the partially or fully protonated forms thereof, cosmetically acceptablesalts thereof_(;) and any combination thereof wherein these Formulas andhomologs thereof have the following structures:

wherein R_(1b), R_(1c), R_(1e), R_(1f), R_(1i), R_(1j) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyi, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached to alinker with or without a terminal amino group; and R_(1h) and R_(1g) areeach independently hydrogen, C₁-C₈ alkyl or a linker group with aprimary, secondary or tertiary amino group attached; and. R_(1a) andR_(1d) are each independently C₁-C₈ alkyl or a linker group with aprimary, secondary or tertiary amino group attached; and the totalnumber of amino groups attached to R_(1a), R_(1d), R_(1g) and R_(1h) is1-4;

wherein R_(3b), R_(3c), R_(3d), R_(3e), R_(3h), R_(3i) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached to alinker with or without a terminal amino group; and R_(3f) and R_(3g) areeach independently hydrogen, C₁-C₈ alkyl or a linker group with aprimary, secondary or tertiary amino group attached; and R_(3a) is C₁-C₈alkyl or a linker group with a primary, secondary or tertiary aminogroup attached; and the total number of amino groups attached to R_(3a),R_(3f), and R_(3g) is 1-3;

wherein R_(4b), R_(4c), R_(4d), R_(4e), R_(4g), R_(4h) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached to alinker with or without a terminal amino group; and R_(4f) is hydrogen,C₁-C₈ alkyl or a linker group with a primary, secondary or tertiaryamino group attached; and R_(4a) is C₁-C₈ alkyl or a linker group with aprimary, secondary or tertiary amino group attached; and the totalnumber of amino groups attached to R_(4a) and R_(4f) is 1 or 2;

wherein R_(6c), R_(6d), R_(6e), R_(6g), R_(6h), R_(6i), R_(6j) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached to alinker with or without a terminal amino group; and R_(6a) and R_(6c) areeach independently a linker group with a cationic moiety attached, thecationic group is quaternary ammonium, imidazolium, pyridinium,oxazolium, or thiazoliumis, and wherein R_(6a) R_(6e) can also eachindependently take on the form of L₁-Q*(-L₂A)_(n), where L₁ and L₂ canbe the same or different linkers, Q* is the cationic moiety, A is anamino group and n is either 1 or 2; and R_(6b) and R_(6f) are eachindependently a hydrogen, alkyl or linker group L with a primary,secondary or tertiary amino group attached; and the total number ofamino groups attached to R_(6a), R_(6b), R_(6e) and R_(6f) is 1, 2, 3 or4 and the total number of cationic moiety attached to R_(6a) and R_(6e)is 1 or 2;

wherein R_(7b), R_(7c), R_(7d), R_(7f), R_(7g), R_(7h), R_(7i), R_(7j),R_(7k) and R_(7m) are each independently hydrogen, alkyl, halogensubstituted alkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy,aryloxy, acyl, halogen, nitro, nitroso, cyano, a heterocyclic moiety,thioether or are attached to a linker with or without a terminal aminogroup; and R_(7a) and R_(7e) are each independently C₁-C₈ alkyl or alinker group with a primary, secondary or tertiary amino group attached;and the total number of amino groups attached to R_(7a) and R_(7e) is 1or 2;

wherein R_(9b), R_(9e), R_(9g), R_(9h), and R_(9f) each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to a linker with orwithout an amino group on the other end of the linker; and R_(9a) andR_(9f) are each independently C₁-C₈ alkyl or a linker group with aprimary, secondary or tertiary amino group attached; and R_(9d) andR_(9e) are each independently hydrogen, C₁-C₈ alkyl, hydroxyl alkyl or alinker group with a primary, secondary or tertiary amino group attached;and the total number of amino groups attached to R_(9a), R_(9d), R_(9e)and R_(4f) is 1-4;

wherein R_(10b), R_(10c), R_(10d), R_(10e), and R_(10i) are eachindependently hydrogen, alkyl, halogen substituted alkyl alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached to alinker with or without a terminal amino group; and R_(10a) and R_(10b)are each independently C₁-C₈ alkyl or a linker group with a primary,secondary or tertiary amino group attached; and R_(10f) and R_(10g) areeach independently hydrogen, C₁-C₈ alkyl, hydroxyl alkyl or a linkergroup with a primary, secondary or tertiary amino group attached; andthe total number of amino groups attached to R_(10a), R_(10f), R_(10g)and R_(10h) is 1-4; and

wherein R_(15b), R_(15c), R_(15d), R_(15e), R_(15g), R_(15h), R_(15k)and R_(15l) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to a linker with or without an amino group on the other end ofthe linker; and R_(15a) and R_(15f) are each independently C₁-C₈ alkylor a linker group with a primary, secondary or tertiary amino groupattached; and R_(15i) and R_(15j) are each independently hydrogen, C₁-C₈alkyl, hydroxyl alkyl or a linker group with a primary, secondary ortertiary amino group attached; and the total number of amino groupsattached to R_(15a), R_(15f), R_(15i) and R_(15j) is 1-4.
 2. The methodof claim 1, wherein the one or more direct dye compounds each comprisetwo incipient cations.
 3. The method of claim 1, wherein the one or moredirect dye compounds each has a molecular weight of less than about1,000 g/mol.
 4. The method of claim 1, wherein the hair colorcomposition has a pH of from about 9 to about
 11. 5. The method of claim1, wherein the hair color composition has a pH of from about 7 to about9. 6, The method of claim 1, wherein an oxidizing agent is appliedbefore or during the application of the hair color composition.
 7. Themethod of claim 6, wherein the oxidizing agent is selected from thegroup consisting of peroxides, perborates, percarbonates, persulfates,oxidant generating enzymes, oxidant generating substrates, andcombinations thereof.
 8. The method of claim 1, wherein the hair color csition further comprises one or more oxidation dyes.
 9. The method ofclaim 1, wherein the chromophore has a structure according to Formula(Xa), Formula (Xf), or Formula (Xg).
 10. The method of claim 9, whereinthe one or more direct dye compounds each comprise two incipientcations.
 11. The method of claim 9, wherein the one or more direct dyecompounds each has a molecular weight of less than about 1,000 g/mol.12. The method of claim 9, wherein the hair color composition has a pHof from about 7 to about
 9. 13. The method of claim 9, wherein anoxidizing agent is applied before or during the application of the haircolor composition.
 14. The method of claim 9, wherein the hair colorco:. sition further comprises one or more
 15. The method of claim 1,wherein the chromophore has a structure according to Formula (Xo). 16.The method of claim 15, wherein the one or more direct dye compoundseach comprise two incipient cations.
 17. The method of claim 15, whereinthe one or more direct dye compounds each has a molecular weight of lessthan about 1,000 g/mol.
 18. The metlrod of claim 15, whe hair colorcomposition has a pH of from about 7 to about
 9. 19. The method of claim15, wherein an oxidizing agent s applied before or during theapplication of the hair color composition.
 20. The method of claim 15,wherein the hair color composition further comprises one or moreoxidation dyes.